Article with Visual Effect and Method of Making

ABSTRACT

A blow molded article formed from a preform having an exterior surface including at least one etched region. The article includes a body portion including one or more walls surrounding an interior space. A cavity region corresponding to the etched region in the preform is disposed on a portion of the article outer surface and a non-cavity region is disposed adjacent the cavity region. The adjacent cavity and non-cavity regions form one or more visual effects and at least one of the one or more visual effects includes a portion having a 95% Delta E Value of at least 3.0.

FIELD OF THE INVENTION

The present invention relates to articles with unique visual effects,preforms for blow molded articles, and methods for making such articlesand preforms.

BACKGROUND OF THE INVENTION

Articles made of thermoplastic materials are popular in variousindustries, including containers for consumer goods, food and beverages.Blow molded packages, such as bottles, are one popular type ofthermoplastic container. Blow molded packages are made by first creatinga preform that is subsequently expanded in a mold, generally with air oranother gas under high pressure, to form the resulting article. Forcertain articles, stretch blow molding is used where the preform issoftened and/or stretched while in the mold prior to being expanded intothe final article.

Although blow molding has been found to be an effective and efficientprocess for manufacturing articles such as containers and the like, therequirements of the process can make it difficult to provide articleswith certain visual and/or tactile features, hereinafter referred to asaesthetic features. For example, it may be desirable to provide anarticle with one or more aesthetic features, such as, for example,visual effects that have a three-dimensional appearance or that have orappear to have some depth or texture. Such features may be desirable inmono-layer articles or in multi-layer articles and may be desirablewhether the surface of the article is smooth or textured. However,typical preform manufacturing and blow molding process often limit theavailable options for the aesthetics of the outer surface of the articlebecause of the steps used to make preforms, the high cost of the moldsfor the blow molding process, and the processing requirements needed toblow the preform into the final article.

Thus, it would be desirable to provide improved aesthetic features onblow molded and other articles. It would also be beneficial to providean improved process for manufacturing blow molded articles to allow fora greater range of aesthetic features. It would also be desirable toprovide an improved method of forming preforms for blow molded articlesthat allows the resulting blow molded articles to have a greater rangeof visual effects and/or to allow such visual effects to be modifiedquickly and cost effectively. Further still, it would be desirable toprovide improved aesthetic features, such as, for example, visualeffects, on blow molded and other articles while keeping the processsimple, cost-effective and scalable to mass manufacture. It would alsobe desirable to provide blow molded articles having dimensional visualeffects with the appearance of depth, dimension (e.g. 3D), or texturewhile maintaining a generally smooth outer surface on the article. Evenfurther, it would be desirable to provide improved visual effects onblow molded and other articles using conventional equipment.

The invention disclosed herein may provide any one or more of thedescribed or other features and/or benefits and such features and/orbenefits may be provided separately or in any desired combination.

SUMMARY OF THE INVENTION

The present invention provides a solution for one or more of thedeficiencies of the prior art as well as other benefits. Thespecification, claims and drawings describe various features andembodiments of the invention, including a blow molded article formedfrom a preform having an exterior surface including at least one etchedregion and at least one non-etched region. The article includes a bodyportion including one or more walls surrounding an interior space, theone or more walls having an article inner surface, an article outersurface, and a wall thickness. The article also includes a cavity regiondisposed on a portion of the article outer surface, the cavity regioncorresponding to the etched region in the preform; and a non-cavityregion disposed on a portion of the article outer surface and adjacentthe cavity region. The adjacent cavity and non-cavity regions form oneor more visual effects, and wherein at least one of the one or morevisual effects includes a portion having a 95% Delta E Value of at least3.0.

The invention also includes a method for making a blow molded articlefrom a preform including: providing a preform of a thermoplasticmaterial, the preform having a body with one or more walls and anopening, wherein at least a portion of the one or more walls of thepreform is etched to form a three-dimensional pattern of cavitiesthereon; and blow molding the preform to form a blow molded articlehaving cavity regions and non-cavity regions that together form one ormore visual effects in at least one wall of the blow molded article, atleast one of the one or more visual effects includes a portion having a95% Delta E Value of at least 3.0.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plan view of a preform in accordance with the presentdisclosure.

FIG. 2 is a cross-section view of the preform of FIG. 1 taken through2-2.

FIG. 3 is a plan view of a preform in accordance with the presentinvention as it is being laser-etched.

FIG. 3A is a cross-sectional view of the preform of FIG. 3 taken throughcross-section line 3A-3A.

FIG. 3B is an enlarged view of portion 60 of the preform shown in FIG.3A.

FIG. 4 is a plan view of a blow molded article in accordance with thepresent invention.

FIG. 4A is cross-sectional view of the preform of FIG. 4 taken throughcross-section line 4-4.

FIG. 4B is an enlarged view of portion 60 of the preform shown in FIG.3A.

FIG. 4C is an enlarged view of portion of a preform in accordance withthe present invention.

FIG. 4D is an enlarged view of portion of a blow molded article inaccordance with the present invention.

FIG. 4E is an enlarged view of portion of a preform in accordance withthe present invention.

FIG. 4F is an enlarged view of portion of a blow molded article inaccordance with the present invention.

FIG. 4G is an enlarged view of portion of a preform in accordance withthe present invention.

FIG. 4H is an enlarged view of portion of a blow molded article inaccordance with the present invention.

FIG. 5 is a plan view of an article in accordance with the presentinvention.

FIG. 6 is a plan view of an article in accordance with the presentinvention.

FIG. 6A is a cross-sectional view of a blow molded article in accordancewith the present invention.

FIG. 6B is a cross-sectional view of a preform for a blow molded articlein accordance with the present invention.

FIG. 7A is a plan view of a blow molded bottle in accordance with thepresent invention with a portion cut out so that the interior of thebottle can be seen.

FIG. 7B is a plan view of a blow molded bottle in accordance with thepresent invention with a portion cut out so that the interior of thebottle can be seen.

FIG. 8 is an enlarged partial cross-sectional view of a wall of apreform in accordance with the present invention.

FIG. 9 is an enlarged partial cross-sectional view of the wall of apreform shown in FIG. 8 shown with cavities therein.

FIG. 9A is an enlarged partial cross-sectional view of portion 9A ofFIG. 9.

FIG. 10 is an enlarged partial cross-sectional view of a wall of a blowmolded article made from the preform shown in FIG. 9.

FIG. 10A is an enlarged partial cross-sectional view of portion 10A ofFIG. 10.

FIG. 11 is an example of an article made in accordance with the presentinvention and including a dimensional visual effect.

FIG. 12 is a cross-sectional view of an exemplary mold for forming aninjection-molded preform.

FIG. 13 is a perspective view of a preform being etched by a laser.

FIG. 14 is a cross-sectional view of a blow mold in accordance with thepresent invention.

FIG. 15 is a plan view of an bottle in accordance with the presentinvention.

FIG. 15A is a magnified top view of the circle 15A of FIG. 15.

FIG. 16 is a magnified top view of a portion of the bottle of FIG. 15.

FIG. 17 is a magnified side view of the portion of the bottle of FIG.16.

FIG. 18 is a magnified top view of the portion of the bottle of FIG. 17.

FIG. 19 is a curve of the averages of the angles between the articlesurface and the normal of the underlying effect structures set forth inthe Example.

FIG. 20 is a curve of the absolute value of the averages of the shown inFIG. 19.

FIG. 21A is an enlarged plan view of Sample No. 1 in the Examples.

FIG. 21B is an enlarged plan view of the sample shown in FIG. 21Arotated 90 degrees.

FIG. 21C is an enlarged plan view of Sample No. 2 in the Examples.

FIG. 21D is an enlarged plan view of the sample shown in FIG. 21Crotated 90 degrees.

FIG. 21E is an enlarged plan view of Sample No. 3 in the Examples.

FIG. 21F is an enlarged plan view of the sample shown in FIG. 21Erotated 90 degrees.

FIG. 21G is an enlarged plan view of Sample No. 4 in the Examples.

FIG. 21H is an enlarged plan view of the sample shown in FIG. 21Grotated 90 degrees.

FIG. 21I is an enlarged plan view of Sample No. 5 in the Examples.

FIG. 21J is an enlarged plan view of the sample shown in FIG. 21Irotated 90 degrees.

FIG. 21K is an enlarged plan view of Sample No. 6 in the Examples.

FIG. 21L is an enlarged plan view of the sample shown in FIG. 21Krotated 90 degrees.

FIG. 21M is an enlarged plan view of Sample No. 7 in the Examples.

FIG. 21N is an enlarged plan view of the sample shown in FIG. 21Mrotated 90 degrees.

DETAILED DESCRIPTION OF THE INVENTION

“Article”, as used herein refers to an individual object for consumerusage, e.g. a container suitable for containing materials orcompositions. The article may be a container, non-limiting examples ofwhich include bottles, tubes, drums, jars, cups, and the like and may beblow molded or formed by another process. The compositions contained insuch a container may be any of a variety of compositions including, butnot limited to, detergents (e.g., laundry detergent, fabric softener,dish care, skin and hair care), beverages, powders, paper (e.g.,tissues, wipes), beauty care compositions (e.g., cosmetics, lotions),medicinal, oral care (e.g., tooth paste, mouth wash), and the like.Containers may be used to store, transport, and/or dispense thematerials and/or compositions contained therein.

“Blow molding” refers to a manufacturing process by which hollowcavity-containing articles are formed. In general, there are three maintypes of blow molding: extrusion blow molding (EBM), injection blowmolding (IBM), and injection stretch blow molding (ISBM). The blowmolded articles of the present invention can be made via EBM, IBM orISBM, or any other known or developed blow molding method, all of whichare referred to herein simply as blow molding. The blow molding processtypically begins with forming a precursor structure or “preform” that isultimately expanded into the final article. The preform, as used herein,can be any shape or configuration, but is often in the general shape ofa tube with at least one open end, or two open ends. Examples ofpreforms include, but are not limited to, parisons (the name often givento precursor structures used in extrusion blow molding), preforms, andother precursor structures used in different blow molding techniques.Preforms, as used herein, can be formed by extrusion, injection,compression molding, 3D printing and other know or developed methods.Injection molding of the preform can be simple injection molding of asingle material, co-injection of two or more materials in a single stepand/or over-molding preformed in two or more steps. The injection stepcan be closely coupled to a blowing step, as in IBM, 1-step ISBM or1.5-step ISBM, or can be decoupled in a secondary operation such as2-step ISBM. During blow molding, a perform or other precursor structureis typically clamped into a mold and a fluid, often compressed air, isdirected into the preform through the opening to expand the preform tothe shape of the mold. Sometimes the preform is mechanically stretchedprior to or at the same time the fluid is introduced (known as “stretchblow-molding”). Also, the perform may be heated or cooled before thefluid is introduced. The pressure created by the fluid pushes thethermoplastic out to conform to or partially conform to the shape of themold containing it. Once the plastic has cooled and stiffened, the moldis opened and the formed article is ejected.

As used herein, a “blow molded article” is an article formed by blowmolding. Such articles have unique physical and structural attributesthat are well known by those of ordinary skill in the art and are notlimited by the particular blow molding method or technique used to makethe article.

As used herein, an “effect pigment” is a “metal effect pigment” or a“special effect pigment.” Metal effect pigments include metallicplatelet-shaped particles that create a metal-like luster by reflectionof light at the surface of the metal platelet-shaped particles. Specialeffect pigments include all other platelet-like effect pigments whichcannot be classified as metal effect pigments. Special effect pigmentsgenerally include platelet-shaped particles (or crystals) such as mica(natural or synthetic), borosilicate glass, alumina flakes, bismuthoxychloride, and silicon dioxide flakes. The platelet-shaped particlesmay be coated with one or more materials including, titanium dioxide,iron oxide, other metal oxides, silicon dioxide, aluminum oxide and/orother oxides. Such coatings may provide, for example, enhanced chromaticstrength, improved reflection or other benefits. Examples of specialeffect pigments include “pearlescent pigments” (also referred to as“pearl luster pigments”), “interference pigments”, and “nacreouspigments”. These pigments can exhibit pearl-like luster as a result ofreflection and refraction of light, and depending on the thickness ofthe coating, they can also exhibit interference color effects.Interference pigments are defined as special effect pigments whose coloris generated completely or predominantly by the phenomenon ofinterference of light. Other effect pigments may provide, for example,multi-color effects (also called goniochromatic), color travel effects,color flop effects, or color-shifting (e.g. where the observed colorchanges with viewing angle) can be provided using layers and/or coatingswith alternating refractive indices.

Effect pigments, including pearlescent and interference pigments aremarketed as such by suppliers including Merck KGaA and BASF SE. Metaleffect pigments are marketed by such suppliers including Eckart andSchlenk AG. Color shifting effect pigments include Colorstream® fromMerck and Firemist® Colormotion from BASF.

The term “etch” as used herein as a noun, refers to the cavity formedwhen material is removed from a surface. As a verb, the terms “etch” and“etching” refers to the act of removing material from a surface. Etchingcan be performed mechanically, chemically and thermally (e.g. laser).Although there is no specific limitation on the maximum or minimum depthof an etch, etching depths are typically in the range of about 0.001 mmto about 2.0 mm, including any depth within the range, such as forexample, 0.010 mm, 0.075 mm, 0.100 mm, 0.200 mm, 0.300 mm, 0.400 mm,0.500 mm, 1.0 mm, 1.5 mm and others.

The term “layer” in the context of the present invention means athickness of material that is generally continuous and typicallyhomogeneous in terms of its chemical makeup. However, it is contemplatedthat any particular layer may have discontinuities and/ornon-homogeneous materials or regions in certain configurations,including but not limited to pigments, effect pigments, dyes and othermaterials within the layer.

The term “opaque” as used herein means the material, layer, article, orportion of the article being measured has total luminous transmittanceof 0%. The total luminous transmittance is measured in accordance withASTM D1003.

The terms “platelet-like shape” and “platelet-like shaped” refer toparticles that have at least one side that is generally planar.Typically, platelet-like shaped particles will have two dimensions thatare significantly larger than a third dimension (e.g. length and widthversus thickness) and are often shaped like disks, rectangularparallelepipeds, regular or irregular polygons. When platelet-likeshaped particles are used in effect pigments, the most prominentgenerally planar surface of the particle can be referred to as the“effect surface”.

The term “translucent” as used herein means the material, layer,article, or portion of the article being measured has total luminoustransmittance of greater than 0% and less than or equal to 90%.

The term “transparent” as used herein means the material, layer,article, or portion of the article being measured has total luminoustransmittance of 90% or more.

Preform:

As noted above, preforms are commonly used in blow molding processes. Anexemplary preform 10 is shown in FIG. 1. The preform 10 has a body 12,and at least one open end 16 having an opening 34. The preform 10 mayalso include a neck or finish 14, and a closed end 18 disposed oppositeof the open end 16. The finish 14 of the preform 10 may include one ormore threads 20 or other structures that can be used in the resultingarticle to engage with a cap or other closure device. The neck 14 canalso include a transfer ring 22 or other structure that can aid in themanufacturing process.

The preform 10 can be used in a blow molding process to provide apreliminary structure that can be transformed into a final article, suchas a blow-molded article or bottle, by means of directing a pressurizedfluid into the open end 16 of the preform 10 while the preform 10 isdisposed in a mold in the shape of the final article (or an interimarticle). Typically, the preform 10 may be heated or otherwisemanipulated mechanically or chemically to soften the material of thepreform 10 prior to introduction of the pressurized fluid to allow thepreform 10 to expand into the shape of the mold without shattering orcracking. More details relating to exemplary blow molding processes inaccordance with the present invention are described below.

Generally, the preform 10 is formed separately from the blow moldingstep. The preform 10 can be formed by any suitable method, including butnot limited to molding, extrusion, 3D printing, or other known ordeveloped processes. The preform 10 may be formed from a single materialor may include layers or regions of different materials. FIG. 2 is anenlarged cross-section of the preform 10 shown in FIG. 1 taken throughsection line 2-2. As shown, the preform 10 includes one or more preformwalls 30, closed end 18 and interior space 36. The preform walls 30 havean inner surface 32 adjacent the interior space 36 and an outer surface33 forming the exterior of the preform 10. Typically, but notnecessarily, the preform walls 30 are between about 1.0 mm and about 6mm thick.

The preform walls 30 are shown in FIG. 2 as having three layers, outerlayer 40, intermediate layer 42 adjacent to, but inward from outer layer40, and inner layer 44. Although three layers are shown, any number oflayers can be used, including a single layer, two or more layers, threeor more layers or any other number of layers. Also, although in FIG. 2the layers are shown to extend throughout the entire length of thepreform 10, any one or more layers may extend only part way through thepreform 10.

The layers 40, 42 and 44 may each have a thickness, T1, T2 and T3. Thethickness T1, T2, and T3 of each layer 40, 42 and 44 may be the same ormay be different from one or more of the other thicknesses. Further, thethickness of any given layer may change throughout the preform 10. Forexample, the thickness of any layer may randomly change, may change in apredetermined pattern, may change in the direction of the length of thepreform 10 and/or may change about the circumference of the preform 10walls 30. The layers may be made of the same material or differentmaterials. They may also be the same or different colors or have thesame or different luminous transmittance. For example, the outer layer40 may be transparent and the inner layer 44 or intermediate layer 42may have a color or be translucent or opaque, although any othercombinations of layers with the same or different luminous transmittanceare contemplated. By including layers with different colors and/ordifferent luminous transmittance, the article formed from the preform 10can have interesting and/or unique aesthetic characteristics.

A preform 10 or article according to the present invention may be formedof a single thermoplastic material or resin or from two or morematerials that are different from each other in one or more aspects.Where the preform 10 has different layers, the materials making up eachof the layers can be the same or different from any other layer. Forexample, the preform 10 or article may comprise one or more layers of athermoplastic resin, selected from the group consisting of polyethyleneterephthalate (PET), polyethylene terephthalate glycol (PETG),polystyrene (PS), polycarbonate (PC), polyvinylchloride (PVC),polyethylene naphthalate (PEN), polycyclohexylenedimethyleneterephthalate (PCT), glycol-modified PCT copolymer (PCTG), copolyesterof cyclohexanedimethanol and terephthalic acid (PCTA), polybutyleneterephthalate (PBCT), acrylonitrile styrene (AS), styrene butadienecopolymer (SBC), or a polyolefin, for example one of low-densitypolyethylene (LDPE), linear low-density polyethylene (LLPDE),high-density polyethylene (HDPE), propylene (PP) and a combinationthereof.

Recycled thermoplastic materials may also be used, e.g., post-consumerrecycled (“PCR”) materials, post-industrial recycled (“PIR”) materialsand regrind materials, such as, for example polyethylene terephthalate(PCRPET), high density polyethylene (PCRHDPE), low density polyethylene(PCRLDPE), polyethylene terephthalate (PIRPET) high density polyethylene(PIRHDPE), low density polyethylene (PIRLDPE) and others. Thethermoplastic materials may include a combination of monomers derivedfrom renewable resources and monomers derived from non-renewable (e.g.,petroleum) resources. For example, the thermoplastic resin may comprisepolymers made from bio-derived monomers in whole, or comprise polymerspartly made from bio-derived monomers and partly made frompetroleum-derived monomers.

The thermoplastic resin can have a relatively narrow weightdistribution, e.g., metallocene PE polymerized by using metallocenecatalysts. These materials can improve glossiness, and thus in themetallocene thermoplastic execution, the formed article has furtherimproved glossiness. Metallocene thermoplastic materials can, however,be more expensive than commodity materials.

The preform 10 can be formed by any known or developed method. Forexample, the preform 10 can be formed by extrusion, injection,co-injection and/or over-molding as well as less conventional techniqueslike compression molding, 3D printing or the like. The preform 10 may beformed such that at least a portion of the preform walls 30 includessome texture, e.g. lines, dots, a pattern, and/or indicia, or they maybe formed to be smooth. Some of the limitations related to texturing thepreform 10 by means of the preform mold can be avoided by the methoddescribed herein and/or by 3D printing of the preform.

The preform 10 may be formed with one or more protuberances 31 orcavities 320 (as shown in FIG. 3A) on at least a portion of the outersurface 33 of the preform wall 30. Such protuberances 31 and/or cavities320 may be formed on the outer surface 33 when the preform 10 isoriginally formed (e.g. in the preform mold), or may be formed at alater time or in a different process. Examples of ways to createprotuberances 31 or cavities 320 on the outer surface 33 of the preform10 after it is formed include, but are not limited to etching, includingbut not limited to laser-etching, mechanical etching, thermal etchingand chemical etching; water jets; cold pressing; hot pressing; milling;etc. The protuberances 31 and/or cavities 320 may also be formed byadding material to the outer surface 33 of the preform 10 during orafter the preform molding process. The protuberances 31 and/or cavities320 may take on any desired shape and may be in the form of a random orpredetermined pattern including lines, dots, curves, letters, numbers,and/or indicia on the outer surface 33.

FIG. 3 shows an exemplary embodiment of a preform 10 that is beinglaser-etched by the beam 50 of laser 52, although any other suitabletechnique may be employed. The laser beam 50 removes a portion of thematerial forming the outer surface 33 of the preform 10 resulting in theprotuberances 31 on the outer surface 33. One advantage of usingpost-formation modification of the outer surface 33 of the preform 10 isthat there are few, if any, limitations with respect to the particularpattern that can be chosen for the protuberances. Further, usinglaser-etching or other easily modified etching methods can also allowfor different preforms 10 from the same mold to have different patternsof protuberances 31 and/or cavities 320 which can significantly reducethe cost of producing articles with different aesthetic features, and/orvisual effects, which in turn, can make production of small numbers ofarticles and even customized articles economically feasible.

FIG. 3A is cross-sectional view of the preform of FIG. 3 taken throughsection line 3A-3A of FIG. 3. The exemplary embodiment shown in FIG. 3has three layers in the preform wall 30. Layer 40 is the outer layer,layer 42 is the intermediate layer and layer 44 is the inner layer. Ascan be seen, the outer layer 40 includes protuberances 31 and cavities320. Although the protuberances 31 are shown as being formed from thematerial of the outer layer 40, it is contemplated that they may beformed from a separate material added to the preform 10 and/or any ofthe layers making up the preform 10. One way to form the protuberances31 is to add a material to the outer surface 33 of the preform 10. A wayto form cavities 320 is to remove material from one or more of thelayers of the preform 10. For example, a laser could be used to formcavities 320 in a layer disposed inwardly of the outer layer 40 inaddition to or alternatively to protuberances 31 and/or cavities 320formed in or on any other layer. Yet another way is to form theprotuberances 31 and/or cavities 320 is to do so in the mold when thepreform 10 is originally formed.

FIG. 3B is an enlarged view of a portion 60 of the preform 10 shown inFIG. 3A. For the purposes of this example, the cavities 320 can beconsidered to have been made by laser etching. However, this example isnot intended to limit the scope of the invention and, as noted above,the protuberances 31 and/or cavities 320 can be formed by any suitablemethod. In the Figure, the depth D represents the depth of the cavity320 from the outer surface 33 of the preform 10. If cavities 320 orprotuberances are formed by adding material to the outer surface 33 ofthe preform 10, the depth D is measured from the outer surface 33 to thetop of the material added to form the cavity 320 or as the depth of anycavity 320 formed fully within the added material if the cavity 320 doesnot extend all of the way through the added material to the outersurface 33 of the preform 10.

The depth D can be the same as or different than the thickness of anylayer. For example, the depth D of the cavity 320 can be the same as thethickness T1 of the outer layer 40 or can be greater than or less thanthe thickness T1 the outer layer 40 and/or any other layer (e.g.pre-etching thickness T3 of inner layer 44 or T2 of intermediate layer42). The depth D of the cavity 320 may be less than the thickness T1 ofthe outer layer 40 if it is desired that the outer layer 40 form theouter surface 33 of the preform 10. Alternatively, the depth D of thecavity 320 may be greater than the thickness T1 of the outer layer 40 ifit is desired for one or more layers other than the outer layer 40 toform a portion of the outer surface 33 of the preform 10. The depth D ofthe etching and/or cavities 320 can affect the aesthetic features 112 onthe resulting blow molded article as can different sizes and shapes ofthe laser beam 50.

Typically, the depth D of the cavities 320 is between about 0.001 mm toabout 2 mm, but any suitable depth D can be used. For example, anycavity or portion thereof can be up to about 90% of the thickness of thepreform wall 30. A cavity 320 or protuberance 31 can take any desiredshape. For example, the shape of the cavity 320 may follow a gaussiancurve, where the cavity 320 is wider at the top and narrower at thebottom. A cavity 320 can also be in the shape of a non-tapered slit withgenerally vertical walls. Still further, the shape of a cavity 320 canfollow other geometries like a reverse taper or barrel shaped taper.Even further, the cavity 320 or any portion thereof can have anasymmetric cross-section.

Laser:

As stated above, one method to create predetermined pattern 54, such asa predetermined pattern 54 of cavities 320 on the preform 10 is bylaser-etching. Any suitable laser can be used to etch the surface of thepreform 10. One example of a laser 52 useful for etching/ablating apreform 10 in accordance with the present invention is a sealed carbondioxide type laser, having power in the range of 40 W to 2.5 kW, and alaser wavelength of 9 microns to 11 microns, or from 9.4 microns to 10.6microns. Such lasers are available from various suppliers, including anLPM1000 module, available in 30 LASERSHARP systems from LasX Industries,Inc. of White Bear Lake, Minn., United States. Other makes and types oflasers are also possible and different power ranges and settings may beused. The laser 52 can include optics that can be used to change theenergy density and/or spot size of the laser beam, as desired.

Article:

Articles in accordance with the present invention can take on a varietyof forms. One form, a blow molded article, such as a bottle, isdiscussed throughout the specification and shown in the drawings.However, it should be understood that other forms are contemplated, andthe scope of the invention should not be considered limited to anyparticular form or type unless specifically articulated by the relevantclaim language.

Articles 100 in accordance with the present invention may be providedwith unique and beneficial characteristics. The characteristics are theresult of unique features relating to the structure of the article 100itself, characteristics of the preform 10, and the method of making thepreform 10 and/or article 100. FIGS. 4-6 show examples of blow moldedarticles 100 in accordance with the present invention. As noted above,the present invention can provide aesthetic features 112 (visual and/ortextural) to articles 100 that were heretofore not attainable and/or notattainable with currently available mass production equipment andtechnology. For example, as shown in FIG. 4, articles 100 of the presentinvention may include a neck 103 with an opening 104 in fluidcommunication with an interior space 107 (shown in FIG. 4A), a base 106,a first shoulder 101 adjacent the neck 103, a second shoulder 102adjacent the base 106 and one or more walls 150 extending between thefirst shoulder 101 and the second shoulder 102. As shown in FIG. 4A, thearticle 100 generally has an article inner surface 132, and an articleouter surface 133. The article 100 may include a texture 110 on thearticle inner surface 132 or article outer surface 133 of the article100. In addition, the outer surface 133 of the article 100 or any othersurface may be printed with aesthetics and/or indicia including, but notlimited to graphics, colors, words, numbers, symbols, etc. Examples ofprinting techniques include but are not limited to laser printing, inkjet printing, contact printing, screen printing, lithographic printing,and combinations thereof.

The articles 100 of the present invention may have one or more layers ofmaterial making up portions or all of the article 100. In multilayerarticles 100, there may be two or more layers. For example, as shown inFIGS. 4A and 4B, article 100 may have a first layer 140 forming thearticle outside surface 133 of the article 100, a third layer 144forming an inside surface 132 of the article 100, and a second layer 142sandwiched between the first layer 140 and the third layer 144, whereinthe layers together make up the entire wall 150 of the article 100 inthat region. Generally, the multilayer region (i.e. the regioncomprising more than one layer) makes up a major portion or the entiretyof the article 100 wall 150 surface, but embodiments are contemplatedwherein at least a portion of the article 100 includes fewer than all ofthe layers disposed in at least another region of the article 100. Forexample, one or more of the layers may not extend the entire distancefrom the neck 103 to the base 106 of the article 100.

The walls 150 of the article 100 can be any suitable thickness. Forexample, the wall thickness TW (shown in FIG. 4A) may range from about0.1 mm to about 3.0 mm, although other thicknesses are possibledepending on the particular process used and the desired end result.Also, the relative thickness of the layers, if any, can be differentfrom each other and can vary throughout the particular layer. That iseach of the layers may have a thickness that is different from the otherlayers or some or all may have thicknesses that are approximately thesame. Generally, each layer is somewhere between 5% and 100%, 5% and75%, 5% and 50%, or 5% and 40% of the total thickness of the articlewall. And, as noted above, different portions of the walls 150 and/orlayers may have different thicknesses, as desired.

One or more of the layers or portions of any layer in the article 100may be transparent, translucent or opaque. Likewise, one or more of thelayers or portions thereof may include one or more pigments or othercolor-producing material. In such instances, one or more of the layersmay be visible through one or more of the other layers. The presence ofa smooth transparent outside layer can help allow for pigments in otherlayers to be visible from outside of the article 100 and can at the sametime provide the article 100 with gloss. Without being bound by theory,it is believed that the presence of a glossy surface at a distance froma translucent or opaque layer that includes pigments can create aneffect of “depth” which can contribute to a premium appearance of thearticle itself. It can also give the appearance that the article 100 ismade from glass or a material other than a thermoplastic material.

As shown in FIGS. 5 and 6, articles 100 in accordance with the presentinvention may include one or more aesthetic features 112. Aestheticfeatures 112 include, but are not limited to features that providevisual and/or tactile properties. Aesthetic features 112 includingtactile properties may include protuberances, variation in surfacetopography, surface roughness, surface friction, and/or other tactileproperties. Aesthetic features 112 including visual effects aregenerally visible by users under ordinary use conditions. However,embodiments are contemplated wherein the visual effects or portionsthereof are visible only under certain circumstances, such as when thearticle 100 is filled with a product or material, partially filled orwhen the article 100 is empty or partially empty. Visual effects mayinclude any visual property, including, but not limited to any one ormore of the following: patterns, indicia, one or more colors, shading,gradation, appearance of depth, as well as other aesthetic andcombinations thereof.

One benefit of the present invention is that it allows aestheticfeatures 112 to be added to blow molded articles, for example injectionblow molded (IBM) articles, injection stretch blow molded (ISBM)articles, and extrusion blow molded articles (EMB) that could nototherwise be achieved. This is important because such IBM and ISBM canbe made from PET, which is often preferred over other materials becausePET is more universally recycled than other clear and glossythermoplastic materials. The present invention allows for IBM and ISBMarticles to be made that have smooth outer surfaces and yet have andvisual elements, such as visual effects 360, that appear to have depth,texture and/or dimension (e.g. 3D). Although EBM articles can beprovided with certain textured surfaces, due to the nature of theextrusion blow molding process (typically using PETG), the range oftextures, and thus, aesthetics, is limited. Also, the resulting productstend to be less easily recycled than IBM and ISBM articles containingonly PET. The “G” in PETG refers to glycol modified PET copolymer inwhich some of the ethylene glycol is replaced with a second glycol,cyclohexane dimethanol (CHDM) and it is generally considered acontaminant in recycling streams and can negatively impact theperformance and processability of PET. Thus, improvements in theaesthetic features of IBM and ISBM articles is highly desirable.

One especially advantageous and unique aspect of the present inventionis that it allows for articles 100 to be formed with a visual impressionof depth, texture and/or dimension on the article outer surface 133 ofthe article 100, even where the article outer surface 133 or portionsthereof are smooth relative to the texture or visual impression oftexture. Referring back to FIG. 4, a relatively smooth article outersurface 133 with a texture-like appearance may be, for example, achievedwhen a texture 110 is formed on the inner surface 132 of the article100, and at least a portion of the one or more layers of the wall 150 ofthe article 100 is/are transparent or translucent. A smooth articleouter surface 133 can be advantageous, for example, when applying alabel 115 to a portion of the article outer surface 133 of the article100, especially when the label 115 is intended to adhere to the articleouter surface 133, such as, for example, pressure sensitive labels,shrink labels, direct object printing, wrap around labels, screenprinting, in-mold labels, transfer labels, pad printing and any otherlabels, printing or materials placed on or adjacent the outer surface133. A smooth article outer surface 133 can also be desirable when thearticle outer surface 133 is to be printed, when a shrink label is used,and/or for other reasons, including “feel”, processing, look, etc.

As shown in FIGS. 4A and 4B, the article 100 may have a texture 110disposed on a portion 120 of the article 100. The texture 110 may createall or a portion of an aesthetic feature 112, as set forth herein. Inthe example shown, the texture 110 is disposed on the inner surface 132of the article, but embodiments are contemplated wherein the texture 110is disposed on the article outer surface 133 and or both the articleinner surface 132 and the article outer surface 133. The texture 110 isshown as being created by variations in the thickness T6 of the innerlayer 144 of the article. The texture 110 is the result of the etchingdone to the preform 10 that was used to form the article 100 and theblow molding process itself.

The aesthetic feature 112 results from the preform 10 from which thearticle 100 is made being manipulated prior to expanding the article 100to its final shape. The aesthetic feature 112 may include etched regions111 and non-etched regions 113. The etched regions 111 correspond to theareas of the article 100 that were etched when the article was a preform10 and not yet expanded to its final shape. The non-etched regions 113are regions of the article 100 that correspond to regions of the preform10 that were not etched prior to being expanded into the final article100. The etched regions 111 may be flush with or extend inwardly oroutwardly from the non-etched regions 113 of the outer surface 133 ofthe article 133. It may be desirable that if the etched regions 111extend inwardly or outwardly from the non-etched regions 113, they do sono more than a pre-determined amount to provide the outer surface 133with a particular topography. For example, limiting the inward oroutward extension of the etched regions 111 can help provide an outersurface 133 that is smooth to the touch and/or can readily acceptprinting and/or a label, or other form of decoration.

As shown in FIG. 4B, the article 100 may have a first layer 140 having afirst thickness T4, a second layer 142 having a second thickness T5, anda third layer 144 having a third thickness T6. The first layer 140 isdisposed outwardly of the third layer 144. The first layer 140 includesthinned regions 152 that are thinner than the thickness T4 of the firstlayer 140 outside of the thinned regions 152. The thinned region 152 ofthe first thickness T4 may be less thick than at least a portion of thesecond thickness T5 and/or third thickness T6 overlying the thinnedregions T4. Thus, the aesthetic feature 112 may be created by variationsin the thickness of one or more of the layers of the article 100 in apredetermined pattern. As shown in FIGS. 4A and 4B, the first thicknessT4 of the article 100 may vary more than the second thickness T5 of thesecond layer 142 and/or the third thickness T6 of the third layer 144through at least a portion of the aesthetic feature 112.

FIGS. 4C-H show different examples of how the wall 150 of an article 100may look due to different etching depths made to the preform 10. FIG. 4Cshows the wall 30 of a preform 10 wherein the depth D of the etching isless than the thickness T1 of the outer layer 40. FIG. 4D shows how thewall 150 of an article formed from the preform 10 of FIG. 4C might lookafter the article 100 is formed. As shown, the portion of the wall 150shown includes three layers, a first layer 140, a second layer 142disposed inwardly of the first layer 140 and a third layer 144 that isdisposed inwardly of the second layer 142. The first layer 140 has aportion corresponding to the etching of the preform 10 that is thinnerthan the non-etched portion of the wall 150. FIG. 4E shows the wall 30of a preform 10 wherein the depth D of the etching is equal to thethickness T1 of the outer layer 40. FIG. 4F shows how the wall 150 of anarticle formed from the preform 10 of FIG. 4E might look after thearticle 100 is formed. As shown, the wall 150 includes three layers, butthe first layer 140 has a portion missing corresponding to the etchingof the preform 10. Thus, at least a portion of the outer surface 133 ofthe article 100 is formed by the second layer 142. FIG. 4G shows thewall 30 of a preform 10 wherein the depth D of the etching is greaterthan the thickness T1 of the outer layer 40. FIG. 4H shows how the wall150 of an article formed from the preform 10 of FIG. 4C might look afterthe article 100 is formed. As shown, the wall 150 includes three layers,but the article outer surface 133 has a portion corresponding to theetching of the preform 10 that is made up of the third layer 144. Anarticle 100 can be formed from any number of layers and can include anynumber of aesthetic features 112 (visual and/or textural) and/orfunctional that have characteristics, e.g. different layers visibleand/or forming the outer surface 133 of the article 100.

FIGS. 5 and 6 are examples of bottles in accordance with the presentinvention. FIG. 5 shows an article 100, such as a bottle, with anaesthetic feature 112 visible on the article outer surface 133. Thearticle has three layers of material forming the wall 150 of the article100. The outer layer of the article 100 is a different color than themiddle layer. The unique aesthetic feature 112 can be at least partiallyattributed to the fact that a portion of an inner layer of the article100 is visible through the outer layer. The aesthetic pattern 112 isformed by laser-etching the preform used to make the article 100.Specifically, the outer layer of the preform is laser-etched in apredetermined pattern 54 and at a predetermined depth to allow the colorof the middle layer of the article 100 to be visible through the outerlayer. In the embodiment shown, the first layer 140 includes a materialthat provides a gloss surface. The article outer surface 133 isgenerally smooth despite the visual impression of texture provided bythe aesthetic feature 112.

The extent to which a particular surface is smooth can be expressed interms of various different surface topography measurements. Twomeasurements that have been found to be particularly helpful incharacterizing the surface topography of preforms and articles inaccordance with the present invention are Maximum Peak/Pit Height (Sz)and Root Mean Square Roughness (Sq) as described below in theMeasurement Methods section of this specification. For example, it maybe desirable to limit the Maximum Peak/Pit Height across some or all ofthe article outer surface 133 and/or the Root Mean Surface Roughness theto provide a surface that is desirable for printing, and/or labeling, orfor other tactile, aesthetic, or functional reasons. For example, it maybe desirable for the Sz of some or all of the article outer surface 133to be less than or equal to 750 microns, 500 microns, 250 microns, 200microns, 150 microns, 100 microns, or 50 microns. Additionally, oralternatively, it may be desirable for some or all of the etched regions111 to have an Sq of a certain value or below. For example, it may bedesirable for some or all of the etched regions 111 to have an Sq ofless than or equal to 10 microns, 8 microns, 5 microns, or 2 microns. Asa result of the process used to form the aesthetic feature 112, such aspredetermined pattern 54, the inner surface 132 may have certaintopological characteristics as well. For example, some or all of theetched regions 111 of the inner surface 132 may have an Sq of greaterthan or equal to about 2 microns, 5 microns, 8 microns, or 10 micronsand the Sz of some or all of the article inner surface 132 may begreater than or equal to 50 microns, 100 microns, 150 microns, 200microns, 250 microns, 500 microns, or 750 microns.

FIG. 6 shows an article 100, a bottle, with an aesthetic feature 112visible on the article outer surface 133. The article has three layersof material forming the wall 150 of the article 100. The outer layer ofthe article 100 is a different color than the middle layer. The uniqueaesthetic feature 112 can be at least partially attributed to the factthat a portion of an inner layer of the article 100 is visible throughthe outer layer. The aesthetic pattern 112 is formed by laser-etchingthe preform used to make the article 100. Specifically, the outer layerof the preform is laser-etched in a predetermined pattern 54 and at apredetermined depth to allow the color of the middle layer of thearticle 100 to be visible through the outer layer. In the embodimentshown, the first layer 140 includes a material that provides a glosssurface. The article outer surface 133 is smooth relative to the visualimpression of texture provided by the aesthetic feature 112.Specifically, the article outer surface 133 or portion thereof that issmooth, for example, may have an Sq of less than or equal to about 10microns, 8 microns, 5 microns, or 2 microns. Additionally, oralternatively, the article outer surface 133 may have a topographycreated by the aesthetic feature 112 having an Sz that is less than orequal to 750 microns, 500 microns, 250 microns, 200 microns, 150microns, 100 microns, or 50 microns. As a result of the process used toform the aesthetic feature 112, the inner surface 132 may have certaintopological characteristics as well. For example, some or all of theetched regions 111 of the inner surface 132 may have an Sq of greaterthan or equal to about 2 microns, 5 microns, 8 microns, or 10 micronsand the Sz of some or all of the article inner surface 132 may begreater than or equal to 50 microns, 100 microns, 150 microns, 200microns, 250 microns, 500 microns, or 750 microns.

For any multi-layer article 100, the article outer surface 133 may beformed solely by the third layer 144 or may be formed partially by thethird layer 144 and at least partially by any other layer. For example,the article 100 may have a wall 150 that has an article outer surface133 formed mostly by the third layer 144 and partially by another layer.This can be the case when the outer layer 40 of the preform 10 is etchedto a depth that an underlying layer is exposed in the final article 100.This can provide the article 100 with unique visual and tactile featuresas the layers may have different characteristics, such as gloss,translucency, color, feel, etc.

Although the above examples are of a multi-layer article, mono-layerblow molded articles are also contemplated. For example, as shown inFIG. 6A, a mono-layered article 100 may be formed from a preform havinga thermally-etched predetermined pattern 54. An aesthetic, functional,and/or texture feature may be incorporated into the wall 150 of thearticle 100 such that it is visible from the exterior of the article100. The aesthetic feature 112 may be formed from variations in thethickness of the wall 150 corresponding to a predetermined pattern 54.The predetermined pattern 54 may include regions or patterns that wereablated from the outer surface 33 or inner surface 32 of the preform 10(an example of which is shown in FIG. 6B) used to create the article100, such as, for example, by laser-etching. The mono-layer,laser-etched, article 100 may have an article outer surface 133 orportion thereof that is smooth, for example, having an Sq of less thanor equal to about 10 microns, 8 microns, 5 microns, or 2 microns.Additionally, or alternatively, the article outer surface 133 may have atopography created by the aesthetic feature 112 having an Sz that isless than or equal to 750 microns, 500 microns, 250 microns, 200microns, 150 microns, 100 microns, or 50 microns. As a result of theprocess used to form the aesthetic feature 112, the inner surface 132may have certain topological characteristics as well. For example, someor all of the etched regions 111 of the inner surface 132 may have an Sqof greater than or equal to about 2 microns, 5 microns, 8 microns, or 10microns and the Sz of some or all of the article inner surface 132 maybe greater than or equal to 50 microns, 100 microns, 150 microns, 200microns, 250 microns, 500 microns, or 750 microns.

The article 100 may be a container or package such as bottle 180 shownin FIGS. 7A and 7B. The bottle 180 may be filled with a composition 182such as a personal care or home care composition. The bottle 180 mayinclude one or more aesthetic features 112 that are enhanced ormitigated by the presence of the composition 182 in the bottle 180. Forexample, a composition 182 in a transparent or translucent bottle 180with a texture 110 on the article inner surface 132 may result in thetexture 110 being more, less or even non-apparent where the composition182 is disposed adjacent the texture 110 than where it is not. In oneexample, a white composition 182 in a transparent or translucent bottle180 with texture 110 on the inner surface may obscure the pattern of thetexture 110 where the composition 182 is disposed adjacent the texture110. However, the texture 110 may be clearly visible in regions wherethe composition 182 is not present, for example, the top portion of thebottle 180 when the bottle 180 is less than half-full of the composition182. Similarly, other forms of color-matching between the bottle-colorand the composition-color (e.g. a blue composition in a blue bottle) mayresult in the aesthetic feature 112 being more or less-apparent duringthe time the product is sold or used. Alternately, the aestheticfeatures 112 of the bottle 180 may be enhanced by the composition 182therein. For example, choosing different colors for the composition 182and the bottle 180 may result in the texture or aesthetic features 112being visually enhanced when the composition 182 is in the bottle 180.Often, colors are described in terms of color-saturation (e.g. L in theL, a, b-scale) and hue, but other color characteristics may also affectthe aesthetics of the bottle-composition combination.

The aesthetic feature 112 can be registered with any label 115, pigment,texture, graphic, or any other textural or aesthetic feature of thearticle 100. For example, it may be desirable to provide the article 100with a region of visual depth, dimension or texture 110 in a particularlocation to help enhance another feature of the article 100. To do so,the aesthetic feature 112 can be registered or provided in apre-determined location such that the aesthetic feature 112 is locatedin the desired location on the final article 100. Additionally, thepresent invention can provide the additional benefit of not having toregister labels and/or printing with certain areas on the article 100because the aesthetic feature 112 can be provided while still allowingfor a generally smooth outer surface 133. Thus, it may provide a morecost efficient and effective to present articles 100 for labeling orfurther decoration, etc. than similar articles with rough or unevenouter surfaces.

The predetermined pattern 54 etched into the preform 10 can be designedso as to provide the aesthetic feature 112 on the article 100 after anydistortion that may result from the blowing of the preform 10 into thefinished article 100. For example, some or all of the features,patterns, indicia and the like comprising a predetermined pattern 54 onthe article 100 may be etched on the preform 10 in a pattern that isdistorted relative to its desired finished appearance, so that thefeatures, patterns, indicia and the like acquire their desired finishedappearance upon being formed into the three-dimensional article 100.Such pre-distortion printing may be useful for indicia such as logos,diagrams, bar-codes, and other images that require precision in order toperform their intended function.

Preforms 10 and articles 100 according to the invention can compriselayers and/or materials in layers with various functionalities. Forexample, an article 100 may have a barrier material layer or a recycledmaterial layer between an outer thermoplastic layer and an innerthermoplastic layer. The article 100 may comprise, for example,additives typically in an amount of from 0.0001%, 0.001% or 0.01% toabout 1%, 5% or 9%, by weight of the article. Non-limiting examples offunctional materials include, but are not limited, to titanium dioxide,filler, cure agent, anti-statics, lubricant, UV stabilizer,anti-oxidant, anti-block agent, catalyst stabilizer, colorants,pigments, nucleating agent, and a combination thereof.

Unique Characteristics when Effect Pigments are Used:

The material making up of any one or more of the layers of the preform10 and article 100 may include one or more effect pigments or othermaterials such as porogens, including, but not limited to themicrodomain-forming liquids, microdomain-forming solids,microvoid-forming solids, and blowing agents described herein. As usedherein the term “porogen” refers to a material which may causegas-filled or vapor-filled microdomains or micropores to occur in apolymer matrix. Examples of porogens include porous solid particleswhich retain at least some of their porosity during processing to form acontainer. Other porogens include solid particles which at leastpartially separate from the matrix upon stretching of a thermoplasticmaterial, resulting in micropore formation. Examples of such solidparticles include calcium carbonate particles which may be coated with afatty acid or salt(s) thereof. Porogens also include blowing agentswhich may vaporize or evolve gas to form micropores. Such materials maybe added to provide a number of different aesthetic effects in thepreform 10 or finished article 100, such as, for example, pearlescence,sparkle, reflection, color change, etc. Surprisingly, however, asdescribed in more detail herein, it has been found that when combinedwith etching, texturing or otherwise modifying the outer surface 33 ofthe preform 10, the inclusion of effect pigments and/or porogens canprovide unique and previously unattainable aesthetic characteristics inthe final article 100. For example, the article 100 can be provided withunique visual effects having the appearance of depth, texture, and/orthree-dimensions. And, except for the novel features and methodsdescribed herein, these aesthetic characteristics can be provided withconventional blow molding equipment and techniques. Further, theseunique aesthetics characteristics can be provided in articles 100 withsmooth, relatively smooth, or substantially smooth outer surfaces 133,which can be a benefit in and of itself. Having a smooth, relativelysmooth, or substantially smooth outer surface 133 may be desirable formany reasons, including because it can allow for easier printing of theouter surface 133, easier labeling, easier handling, better tactilefeel, and other benefits.

The preform 10 may comprise from about 0.01%, to about 5.0%, preferablyfrom about 0.05% to about 1.5%, and more preferably from about 0.1% toabout 0.5%, of a microdomain-forming liquid. Without being bound bytheory, the liquid is believed to be finely dispersed in thethermoplastic material due to the high shear conditions duringcompounding of the masterbatch and/or injection molding of the pre-form.Because the liquid is immiscible with the thermoplastic resin, it formsfinely dispersed droplets or phase-separated microdomains within thethermoplastic material. To minimize interfacial energy, the microdomainstend to be spherical in shape when formed. However, during the injectionand blow molding processes, the microdomains may change shape. If thethermoplastic material undergoes uniaxial shear or stretch in aparticular zone or region, the microdomains may become rod-like,sausage-shaped or ellipsoidal in that region or zone. If thethermoplastic material undergoes biaxial stretch in a particular zone orregion, then the microdomains may become disc-shaped or plate-like inthat region or zone. These and different shapes may be formed dependingon the nature of the extension or stretching of the thermoplasticmaterial. Different fluid-containing microdomain shapes may be disposedin different regions or zones within the preform 10 or article 100.

Microdomain-forming liquids may comprise silicone oils, hydrocarbonoils, liquid polyfluorinated compounds, liquid oligomers, polyalkyleneoxides, ethylene glycol, propylene glycol water, ionic liquids, andmixtures thereof. Some or all of the molecules of the microdomainforming liquid may be linear, cyclic or branched. Some or all of themolecules of the microdomain-forming liquid may contain functionalgroups. Examples of such functional groups include ester, ether, amine,phenyl, hydroxyl, carboxylic acid, vinyl, and halogen groups. A moleculemay contain one or more functional groups and a microdomain-formingliquid may comprise molecules with different functional groups. Specificexamples of microdomain-forming liquids include linear, branched andcyclic polydimethyl siloxane or other polydialkyl or polydiarylsiloxanes. Suitable siloxane liquids include linear or branchedpolydimethylsiloxane homopolymers. Hydrocarbon oils include mineral oils(C15-C40) or liquid paraffins. Polyfluorinated compounds includeperfluorocarbon compounds such as perflouorooctane as well asfluoropolyethers such as Fomblin® oil. Liquid oligomers include lowmolecular weight hydrocarbon compounds such as polyisoprene orpolyisobutylene. Other liquid oligomers include polyalkylene glycolssuch as low molecular weight polyethylene glycol. An examplethermoplastic material is polyethylene terephthalate (PET), and anexemplary microdomain-forming liquid is hydroxyl-terminatedpolydimethylsiloxane.

The preform 10 may comprise from about 0.10%, to about 20%, preferablyfrom about 1.0% to about 10%, and more preferably from about 1.0% toabout 5.0%, of a microdomain-forming solid material or microvoid-formingsolid material. The material is dispersed within a thermoplasticmaterial in the form of small solid particles, the particles typicallyhaving a number-average largest dimension of about 1 micron or less. Theparticles may comprise inorganic material such as calcium carbonate, ororganic material such as poly (methyl methacrylate). Without being boundby theory, the microvoid-forming solid particles are believed to befinely dispersed in the thermoplastic material due to the high shearconditions during compounding of the masterbatch and/or injectionmolding of the pre-form. The solid material may melt during compoundingof the materbatch to form liquid droplets, but re-solidifies uponcooling to 25° C. to form phase-separated finely-dispersed solidparticles within the thermoplastic material.

It is believed that microvoid-forming solids, upon stretching of thethermoplastic material, e.g. during the blow molding process, at leastpartially detach from the thermoplastic material matrix to form discretemicrovoids within the thermoplastic material. A microvoid, as usedherein, can encompass both the gas-filled microvoid and any solidmicrovoid-forming particle(s) therein. The microvoid-forming solidparticles may be treated or coated to facilitate detachment from thethermoplastic polymer matrix upon stretching. For example, the particlesmay be at least partially coated with a relatively thin layer of a fattyacid or salt thereof such as stearic acid or calcium stearate. Examplesof other treatments or coating materials include fluoro compounds andsilicone compounds. Examples of inorganic microvoid-forming solidparticles include calcium carbonate, silica (including ground,precipitated and/or fumed silica), alumina, titania, clays, bariumsulfate, and the like, and mixtures thereof. Examples of organic ororganosilicon microvoid-forming solid particles include polysiloxanewaxes, hydrocarbon waxes, polyalkylene oxide waxes, polystyrene,polyesters such as polycarbonate, polyolefins, poly(meth) acrylates,polymethylpentene, liquid crystalline polymer (LCP), and other solid orwaxy polymers, and mixtures thereof. An exemplary embodiment includes amicrovoid-forming solid is calcium carbonate in a polyethyleneterephthalate (PET).

Microdomain-forming solids, different than microvoid-forming solids, arebelieved to soften during the blow molding process. As such, they tendnot to detach from thermoplastic polymer matrix in which they areimbedded and do not create microvoids. Examples of microdomain-formingsolids include, but are not limited to elastomers and other cross-linkedpolymers and PET.

The preform 10 may comprise from about 0.01%, to about 5.0%, preferablyfrom about 0.05% to about 1.5%, and more preferably from about 0.1% toabout 0.5%, of a microvoid-forming blowing agent. Blowing agents may besolid or liquid under ambient conditions. Without being bound by theory,blowing agents are believed to become finely dispersed or dissolved inthe thermoplastic material due to the high pressure and high shearconditions during compounding of the masterbatch and/or injectionmolding of the pre-form. Blowing agents may be miscible or immisciblewith the thermoplastic resin. Upon a triggering event such as heating,pressure reduction, or change in pH, the blowing agent evolves vapor orgas to form a microvoid within the thermoplastic material matrix. Themicrovoids tend to be spherical in shape when formed. However, duringthe blow molding process, the microvoids may change shape. If thethermoplastic material undergoes uniaxial stretch in a particular zoneor region, the microvoids may become rod-like, sausage-shaped orellipsoidal in that region or zone. If the thermoplastic materialundergoes biaxial stretch in a particular zone or region, the microvoidsmay become disc-shaped or plate-like in that region or zone. Differentshapes may be formed depending on the nature of the extension orstretching of the thermoplastic material and a preform 10 or article 100may have different fluid-containing microvoid shapes in differentregions or zones.

Blowing agents may comprise compounds such as pentane or hexane whichare volatile liquids under ambient conditions, but which boil orvaporize under process conditions which may include increasedtemperature and/or reduced pressure. Alternatively, bowing agents may besolids under ambient conditions but evolve vapor or gas when heated orsubjected to other triggering events. Examples of such materials includepentane, sodium bicarbonate, azo compounds such asazobisisobutyronitrile, peroxy compounds such as dibenzoyl peroxide, andthe like.

The effect pigment, microdomain-forming material, microvoid-formingsolid and microvoid-forming blowing agent may include or formplatelet-like shaped particles or regions (hereinafter “effectstructures”) in one or more of the layers of the preform 10. FIG. 8shows a partial cross-section of a preform wall 30 wherein the materialmaking up the wall 30 includes a multiplicity of effect structures 300.The effect structures 300, as shown in FIG. 8, each have an effectsurface 310, which is the most prominent generally planar surface of theeffect structure 300. Each effect surface 310 has a “normal” N whichrepresents an imaginary line that is perpendicular to the effect surface310. The normal N of any particular effect structure 300 can becalculated as set forth in the Measurements Methods section, below.

As can be seen in FIG. 8, the effect surfaces 310 of the effectstructures 300 may be aligned generally parallel to the outer surface 33of the preform 10 at least adjacent the outer surface 33. Accordingly,the orientation of the normal N of the effect surfaces 310 is generallyperpendicular to the outer surface 33 of the preform 10 at least in askin region 315 adjacent the outer surface 33. This alignment is typicalwhen the preform 10 is formed by extrusion or extrusion molding whereinthe orientation of the effect structures 300 has not been otherwisealtered.

FIG. 9 shows how the outer surface 33 of the preform 10 may bemanipulated, for example, by laser etching or other means, to form oneor more cavities 320 in the outer surface 33 of the preform 10. Thecavity 320 or cavities 320 may form a three-dimensional pattern 325 onthe outer surface 33 of the preform 10. Also, as shown, the effectstructures 300 that remain after the manipulation of the preformgenerally tend to remain oriented as they were prior to themanipulation.

As shown in FIG. 9A, each cavity 320 has a width W, a cavity length (notshown), a cavity center CC, and at two opposed cavity sides CS. Thecavity length is the longest dimension of the cavity 320 and the cavitywidth W is the shorter dimension of the cavity 320 generallyperpendicular to the cavity length. If the cavity 320 has noperpendicular dimensions that are different from each other, then thecavity width W should be taken as the shortest dimension in theparticular region being evaluated and the cavity length is perpendicularto the cavity width W. The cavity center CC is located at the center ofthe cavity in the width W dimension (i.e. equidistant between the cavitysides CS). Each cavity 320 has a cavity central portion 322 centeredaround the cavity center CC. The cavity central portion 322 has acentral portion width CPW that is ½ the width of the cavity. Each cavity320 also includes two cavity side portions 324 disposed on oppositesides of the cavity central portion 322. The cavity side portions 324have a side portion width SPW that is equal to the central portion widthCPW and extend outwardly from the central portion 322 beyond the cavitysides CS. Extending outwardly (away from the cavity center CC) from eachcavity side portion 324 is a non-cavity portion 323 that has anon-cavity portion width NPW that is the same as the central portionwidth CPW and the side portion widths SPW.

FIG. 10 shows how the effect structures 300 in at least the skin region315 can be reoriented during the blowing step of the blow moldingprocess when the preform 10 is transformed into an article 100. Duringthe blowing process, the cavities 320 of the preform 10 are transformedinto corresponding cavity regions 330 in the article 100. As shown inFIG. 10A, each cavity region 330 includes a cavity central region 332that, after blowing, corresponds generally to the central portion 322 ofthe preform 10 and at least one cavity side region 334 that, afterblowing, corresponds generally to the side portion 324 of the preform10. Like the cavities 320, the cavity regions 330 each have a cavityregion width CRW, a cavity region length (not shown), a cavity regioncenter CRC, and at two opposed cavity region sides CRS. The cavityregion length is the longest dimension of the cavity region 330 and thecavity region width CRW is the shorter dimension of the cavity region330 generally perpendicular to the cavity region length. If the cavityregion 330 has no perpendicular dimensions that are different from eachother, then the cavity region width CRW should be taken as the shortestdimension in the particular region being evaluated and the cavity regionlength is perpendicular to the cavity region width CRW. The cavityregion center CRC is located at the center of the cavity region 330 inthe width W dimension (i.e. equidistant between the cavity region sidesCRS). Each cavity region 330 has a cavity central region 332 centeredaround the cavity region center CRC. The cavity central region 332 has acavity central region width CCRW that is ½ the cavity region width CRW.Each cavity region 330 also includes two cavity side regions 334disposed on opposite sides of the cavity central region 332. The cavityside regions 334 have a side region width SRW that is equal to thecavity central region width CCRW and extend outwardly from the centralregion 332 beyond the cavity region sides CRS. Extending outwardly (awayfrom the cavity region center CRC) from each cavity side portion 334 isa non-cavity region 333 that has a non-cavity region width NRW that isthe same as the cavity central region width CCRW and the side regionwidths SRW.

As shown, the orientation of the effect surfaces 310 of the effectstructures 300 disposed outside of the cavity regions 330, for examplein the non-cavity regions 333, remains generally unchanged from theorientation that they had along the outer surface 133 of the preform 10prior to blowing the preform 10 into the article 100. Specifically, theeffect structures 300 disposed in the non-cavity regions 333 andadjacent the outer surface 133 of the article 100 remain orientedgenerally parallel to the outer surface 133 of the article and theirAverage Normal Orientation is generally perpendicular to the outersurface 133. At least some of the effect structures 300 disposed in thecavity side regions 324, however, are oriented such that the orientationof their normal N is at an angle 355 other than perpendicular to theouter surface 133 of the article 100. For example, the at least some ofthe effect surfaces 310 of the effect structures 300 in the cavity sideregions 324 may be disposed at an angle 355 having an absolute value ofbetween about: 3 degrees, 4 degrees, 5 degrees, 6 degrees, 7 degrees, 8degrees, 9 degrees, 10 degrees; and 90 degrees, 89 degrees, 87 degrees,50 degrees, or 30 degrees from perpendicular to the outer surface 133 ofthe article 100 when measured as set forth in the Measurement Methodssection, below. Also, depending on the geometry of the cavity 320 priorto blowing the preform 10 into the article 100, at least some of theeffect surfaces 310 of the effect structures 300 disposed in the cavitycentral regions 332 may be oriented generally parallel to the outersurface 133 of the article, and their normal N oriented generallyperpendicular to the outer surface 133.

It has been found that selectively varying the orientation of the effectsurfaces 310, in at least some regions, can provide unique andunexpected aesthetic features 112 on the article 100. Specifically, ithas been found that selectively varying the orientation of the effectsurfaces 310 can provide a visual effect 360, an example of which isshown in FIG. 11. The visual effect 360 may be, for example, adimensional visual effect (e.g. providing the viewer with the perceptionof depth, texture, and/or three-dimensions) or otherwise. The shape ofthe visual effect 360 on blow molded articles 100 can be random orpredetermined. For example, visual effect 360 having a predeterminedshape can be the same as or similar to that of the three-dimensionalpattern 325 of cavities 320 on the preform 10 and can correspond to alocation on the article 100 that corresponds to the location of thethree-dimensional pattern 325 on the preform 10 or can be otherwiseplanned prior to its formation. Of course, there will typically be somechange in shape and dimensions between the preform 10 and article 100,but one can typically determine which cavities 320 form which visualeffects 360 or portions thereof. Random visual effects 360 do notcorrespond to any predetermined pattern associated with the preform 10.

An especially useful feature of the visual effect 360 is that it can beprovided even in embodiments where the outer surface 133 of the article100 is relatively smooth. As noted above, this can provide severalbenefits, including ease of labeling and printing on the outer surface133, tactile benefits, visual benefits, handling benefits, manufacturingbenefits and an unexpected sensory experience for the user. Further, thevisual effect 360 can be used in combination with other aesthetic andtextural elements to provide even more unique and desired effects.Another useful aspect of the visual effect 360 of the present inventionis that it can be predetermined (i.e. user can choose the pattern of thevisual effect) and intentionally provided by the methods describedherein, including etching the preform 10 and/or otherwise mechanicallyor chemically manipulating the outer surface 33 of the preform 10 toprovide one or more cavities 320. Thus, the unique and unexpected visualeffect can be incorporated into articles manufactured on commonly usedblow molding equipment.

FIG. 11 represents a photograph of an article 100 in accordance with thepresent invention. The article 100 includes an aesthetic feature in theform of a dimensional visual effect 360, as set forth herein. Thearticle 100 shown has a generally smooth outer surface 133, but thedimensional visual effect 360 provides the article 100 with anappearance of texture, three-dimensions, and/or depth. Such aestheticqualities are often associated with high-quality and luxury goods andmay be preferred by consumers over goods with less unique and/or lessaesthetically pleasing aesthetic features 112.

One way to characterize an aesthetic feature including a visual effect360 is in terms of visual contrast. For example, Delta E is often usedto measure the magnitude of contrast within a sample. A 95% Delta EValue, as measured and described herein can be used to measure the pointto point contrast between different regions of an article, such as ablow molded article.

Specifically, it can be used to measure visual effects 360 thatcorrespond to an etched region of the preform from which the article wasmade and include adjacent cavity and non-cavity regions disposed on theouter surface 133 of an article 100. Visual effects having a 95% Delta EValue of at least 3.0, 4.0, 5.0, 5.5, 6.0, 8.0, 10, 12, 15, 20, 25, 30,40, 50, or 100, or between 3.0 and 350, or 5.0 and 100 can provideespecially pleasing aesthetic properties. 95% Delta E values for visualeffects 360 below 3.0 may be difficult for the human eye to perceive andmay not provide the desired aesthetic properties made possible by thepresent disclosure.

Method of Making Blow Molded Article:

As noted above, the article 100 of the present invention can be madeblow molding, including, but not limited to EBM, IBM or ISBM. In suchmethods, the article 100 is formed from a preform 10, such as the oneshown in FIG. 1. The preform 10 can be made by any known method,including injection, 3D printing or any other suitable method. FIG. 12shows an example of a preform 10 in an injection preform mold 200 afterthe material making up the preform 10 has been injected into the preformmold cavity 215 of the preform mold 200 and the preform 10 has beenformed into the desired shape. The material making up the preform 10 isinjected into the mold through orifice 210. After the material is cooledor otherwise modified such that the preform 10 can maintain its shape,the preform 10 is removed from the mold 200. The preform 10 may besubjected to any number of post-molding techniques, including, but notlimited to chemical treatments, heating, cooling, light, mechanicalmanipulation, such as, for example, cutting, etching, scraping, bending,coating, etc. These techniques can help provide the preform 10 and/orfinal article 100 formed from the preform 10 desired properties.

In accordance with the present invention, the outer surface 33 of thepreform 10 may be provided with a preform texture, such as, for example,in a pattern such as predetermined pattern 54. Although the preformtexture could be provided by the preform mold 200, as noted above, suchprocesses are very limited in the preform textures that they can createdue to the requirement that the preform 10 be removed from the mold 200.As such, it is preferred that the preform 10 be provided with thepreform texture after it is removed from the mold 200. As shown in FIG.13, the preform 10 may be laser-etched by one or more lasers 52. Thelaser(s) 52 can direct one or more laser beams 50 to modify or remove aportion of the outer surface 33 of the preform 10. The material ablatedor removed can create a pattern and/or a preform texture on the outersurface 33 of the preform 10. The predetermined pattern 54 or preformtexture can include any number of lines, shapes, dots, curves, indicia,letters or combinations thereof. Any portion of the outer surface 33 ofthe preform 10 may be laser-etched or otherwise modified and themodification process can take place at one time or in multiple differentsteps. The preform 10 may be rotated about its longitudinal axis Lduring etching to allow the etching device to etch the outer surface 33about the circumference of the preform 10 or the etching device may berotated about the preform 10, or both can be rotated.

Once the desired preform texture or pattern is applied to the preform10, the preform may be moved to a blow molding step to form the finalarticle 100 or may be stored or otherwise treated for differentproperties. Generally, just prior to the blow molding step, the preform10 is heated or otherwise treated to soften it from a hardened state.This allows the preform 10 to be more easily blown into the shape of thefinal article 100. Often, the preform 10 is heated by lamps, hot air,radiation or convection, but other methods of heating the preform 10 canbe used. When the preform 10 is ready to be “blown” or expanded into theshape of the final article 100, it is placed into a blow mold, such asfor example, the one shown in FIG. 14. The blow mold 250 has a cavity260 formed by walls 270. The cavity 260 is the shape of the finalarticle 100. The walls 270 may be smooth or may have some texture. Thepreform 10 in the mold 250 is expanded such that the walls 30 of thepreform 10 contact the walls 270 of the blow mold 250 and take the shapeof the cavity 260. Generally, the preform 10 is expanded by forcing airor another fluid into the opening 34 of the preform through the open end16 of the preform. If desired, a vacuum created in the cavity 260 canassist the expansion of the preform 10. Once the preform 10 is expandedinto the shape of the mold 250 and thus, the final article 100, thearticle 100 can be cooled and the blow mold 250 can be removed. Thearticle 100 can be subjected to additional processing steps, includingbut not limited to inspection, removal of imperfections, cleaning,filling, labeling, printing, and sealing.

It is possible to configure the blowing process such that some or all ofthe preform texture creates a texture 110 of the article 100.Surprisingly, the blow molding process can be configured to create thetexture 110 on the inner surface 132 of the article 100, the oppositesurface of the wall 150 where it was originally etched or otherwisecreated. This is especially surprising for thermal etching on theexternal surface of the preform 10. In order to reach temperaturessufficient for thermal ablation and material vaporization, typically azone of melted or heat affected material is generated. This melted orheat affected zone can create thermally induced crystallization on theexternal surface. Crystallized material can resists stretching andreforming to the surface of the blow cavity and may rebound from thesurface of the blow mold. To help create a smooth outer surface 133, theamount of thermal crystallization on the external surface should becontrolled (via efficient ablation on the external surface), and theblowing parameters should be optimized for the desired end result. Forexample, it may be helpful to 1) minimize additional thermalcrystallization on the external surface, 2) optimize the strain inducedcrystallization, and 2) set the material in the mold to avoid concave orconvex surfaces in the transition from thick to thin surfaces.

According to the present invention, it has been found, for example, ifthe preform 10 is laser-etched on the outer surface 33, the finalarticle 100 can have a texture 110 corresponding to the laser-etchingpattern on its inner surface 132. This transfer of the preform textureto the inner surface 132 of the article 100 can allow the article 100 tohave unique and aesthetically pleasing features compared to previouslyknown articles 100. One example, as described in more detail above, is abottle having a smooth article outer surface and an aesthetic feature112, such as visual effect 360, that gives the appearance of thickness,depth and/or texture to the bottle. Such aesthetic features 112 can makethe bottle more attractive and more consumer preferred. Additionally,because the article 100 can be provided with a smooth article outersurface 133, it can be more easily labeled and/or have printing appliedthereto. Further still, because the method provides a way to add atexture, pattern or functional feature to the preform 10 after it is outof the preform mold 200, it can significantly simplify the process formaking complex features on the end article 100. This also allows for thefunctional and/or aesthetic features of the end article 100 to bechanged despite the preform 10 being from the same preform mold 200 andallows for much quicker and more efficient changes to the overallaesthetics, texture or functional features of the article 100 becausenew preform molds 200 are not needed if it is desired to change theresulting article 100. Thus, small productions batches and evencustomized articles become economically feasible.

In addition to the above, if effect structures 300 are incorporated intothe preform 10, unique visual effects 360 may be provided in the article100. The method used to produce such visual effects 360 is the same asset forth above for other aesthetic features 112 except that amultiplicity of effect structures 300 are incorporated into thematerial(s) making up the wall(s) 30 of the preform 10. In one exemplaryand non-limiting embodiment, the preform 10 includes a single-layer ofmaterial having an effect pigment included therein. The effect pigment,and thus the walls 30 of the preform 10 included a multiplicity ofeffect structures 300 each having an effect surface 310. The normals Nof the effect surfaces 310 are aligned generally perpendicular to theouter surface 33 of the preform wall 30, at least adjacent the outersurface 33, after the preform 10 is formed. The outer surface 33 of thepreform wall 30 may be etched, for example, with a laser 52 resulting inseveral cavities 320 in the outer surface 33 of the preform 10. Theeffect surfaces 310 of the effect structures 300 adjacent the outersurface 33 remain aligned generally parallel to the outer surface 33(their normals N being generally perpendicular to the outer surface 33)after etching and prior to the preform 10 being blown into the article100.

Blow molding of the etched preform 10 including effect structures 300into an article 100 allows the user to reorient at least some of theeffect surfaces 310 of the effect structures 300 into a predeterminedpattern that can provide a desired visual effect 360. For example, theeffect surfaces 310 of the effect structures 300 adjacent the outersurface 133 of the article 100 remain aligned generally parallel to theouter surface 133 of the article 100, except in the cavity side regions334 of the cavity regions 330. However, at least some of the normals Nof the effect surfaces 310 of the effect structures 300 disposed in thecavity side regions 334 are oriented differently than the normals N ofthe effect surfaces 310 of the effect structures 300 located outside ofthe cavity regions 330 and at least some of those located fully withinthe cavity central regions 332. Rather than being oriented generallyperpendicular to the outer surface 133 of the article 100, at least someof the normals N to the effect surfaces 310 of the effect structures 300disposed in the cavity side regions 334 are at an angle fromperpendicular to the outer surface 133. Specifically, on average, theorientation of the normal N of the effect surfaces 310 of the effectstructures 300 disposed in, for example, the cavity side regions 330,have an absolute value angle 355 of between about: 3 degrees, 4 degrees,5 degrees, 6 degrees, 7 degrees, 8 degrees, 9 degrees, 10 degrees; and90 degrees, 89 degrees, 87 degrees, 50 degrees, or 30 degrees fromperpendicular to the outer surface 133 of the article 100 when measuredas set forth in the Measurement Methods section, below. Of course, otherangles 355 are contemplated for the orientation of the effect structures300, but those set forth above have been found to be particularlyeffective producing a visual effect 360 on the article 100.

It has been found that articles including at least two regions ofdifferent Average Normal Orientations (calculated as set forth in theMeasurement Methods section, below) of effect structures 300 can providedesirable visual effects 360. For example, an article 100 having aregion having a first Normal Average Orientation and a region having asecond Average Normal Orientation, wherein the absolute value of thedifference between the two is greater than about 3, 4, 6, 7, 8, 9, 10,12, 14, 16, 18, 20, 25, 30, 35, 40, 50 can provide desirable and uniquevisual features on the article 100. This absolute value of thedifferences is referred to herein as the Local Orientation Index (“LOI”)for a particular visual effect 360 or portion thereof. Preferably, theLOI is at least 3 as that is consistent with the minimum perceptible byan unaided human eye. However, the LOI can be any number that providesthe desired effect.

If desired, it is also possible to measure the LOI of regions within thevisual effect 360 that are not adjacent the boundary 515 as compared toregions outside of the visual effect 360. The same method fordetermining LOI is used as described in the Measurement Methods section,herein, except that a region within the visual effect 360 that is notadjacent the boundary 515 is compared to a region outside the visualeffect, as described in the LOI method. It has been found that forcertain visual effects 360, the LOI of such regions within the visualeffect 360, but not adjacent the boundary 515 as compared to regionsoutside the visual effect 360 may be zero, close to zero, below 4, below3, below 2, or below 1. This is because the Average Normal Orientationof the effect structures 300 within the visual effect 360 and notadjacent the boundary 515 may be equal to or about equal to the AverageNormal Orientation of the effect structures 360 outside of the visualeffect 360. Without being bound by theory, it is theorized that such isthe case because the effect structures 300 in portions of the visualeffect 360 corresponding to the cavity central portion 322 of thepreform 10 are not reoriented during the blow molding process and thus,remain in an orientation similar to the effect structures 300 disposedoutside of the visual effect 360.

The depth and width of any particular cavity 320 can impact the visualimpression of the visual effect 360. Typically, the width W of a cavity320 should be at least 0.015 mm so as to ensure the resulting visualeffect 320 is easily visible. The depth D of the cavity (measured thesame as the depth of an etch) can be any suitable depth, but istypically between about 0.001 mm to about 2 mm; between 0.01 mm to about1 mm; or from about 0.08 mm to about 0.5 mm. The orientation of thewalls of the cavity 320 as compared to the surface of the preform 10 canbe any suitable angle.

The type and amount of effect pigment included in any material of thepreform can be chosen based on the desired look of the article 100including the visual effect 360. In general, it is more cost effectiveto include more smaller particles than fewer larger particles, but nospecific particle size or shape is required. Non-limiting examples ofparticle sizes include those with dimensions from about 1 micron toabout 700 microns in length and a thickness of between about 5 nm toabout 1200 nm. Besides the effect pigment(s), other materials may beincluded in the material that makes up the preform 10, includingopacifiers, toner pigments, additives, dyes and the like.

Measurement Methods Layer Thickness:

Layer thickness is measured with an industrial microscope, such asOlympus BX Series Optical Microscope having an accuracy of 0.003 mm, attwo or more locations in the region of the article where the layerthickness is measured.

Wall Thickness:

Wall thickness is measured with a digital micrometer, such as a Shinwa79523 Digital Micrometer having an accuracy of +/−0.003 mm, at two ormore locations in the region of the article where the wall thickness isto be measured.

Average Normal Orientation and Local Orientation Index:

The method set forth herein describes how to measure the normalorientation of effect structures disposed within a layer of material aswell as the Average Normal Orientation of effect structures in a definedregion and the LOI of a particular sample. To help better understand themethod, a brief summary is set forth here and then a specific example isdisclosed in Example 1, below.

Before determining the Average Normal Orientation of any group of effectstructures or the LOI of any portion of an article, it is important toidentify the particular regions of the article that will be measured andthe effect structures within the measured region that will be analyzed.Thus, article 100, such as bottle 180 shown in FIG. 15 is visuallyinspected by a human having 20/20 vision (or the equivalent due tocorrection by glasses, contact lenses or surgery) to find a location onthe wall sample from the wall 150 of the bottle 180 including a visualeffect 360. The visual effect 360 chosen should be located so as not tocompletely overlap the neck 103, first shoulder 101, second shoulder 102or base 106 of the bottle 180, and if possible, not overlap at all withany of such portions or other irregularities in the outer surface 133 ofthe bottle 180. Once the visual effect 360 is chosen, a suitable portionof the visual effect 360 should be identified that has a visuallyperceptible boundary 515, as shown in FIG. 15A, between the visualeffect 360 and a portion of the bottle 180 free from the visual effect360. The sample portion 500 of the bottle 180 to be analyzed shouldinclude the suitable portion of the visual effect 360 as well as theadjacent portion of the wall 150 of the bottle 180 that does not includethe visual effect 360. In certain instances, the sample 505 taken fromthe sample portion 500 may include more than one boundary 515. In suchinstances, the LOI can be measured for a single boundary 515 or anynumber of the boundaries 515 in the sample 505. The sample portion 500should be generally rectangular in shape where the short dimension isparallel to the visual effect boundary 515 and the long dimension isperpendicular to the visual effect 360. The sample portion 500 should becarefully removed from the bottle 180 such that it is not deformed ordamaged and so that it can be further cut into the specific sample size,such as sample 505 shown in FIG. 16, to be analyzed.

Once the sample 505 is obtained, it is scanned with a ComputedTomography (CT) system (equipped with a microscope, as needed) at asufficient resolution to characterize the shape of the effect structures300 therein. The x-ray energy and contrast mode of the CT is set tooptimize the signal due to the effect structures 300 versus the signalfrom the material making up the wall 150 of the article 100 (e.g.plastic or polymeric material). Because the CT data may contain “noise”or “artifacts” and the sample 505 may contain secondary pigmentation oradditives based on isotropic particles (for example, traditionalpigments and/or reheat additives), to enable identification of an effectstructure 300, it is first important to characterize the general shapeparameters of the effect structures 300. The shape parameters of theeffect structures 300 may be obtained from the CT data, but theparameters may be supplemented by or obtained from the manufacturer'sspecifications or other imaging systems and methods.

After the shape parameters of the effect structures 300 are known, theorientation of the effect structures 300 within the sample 505 can bedetermined. The orientation information can be obtained from a CT scantaken of the sample 505. The CT scan can be the same as that which isused to characterize the shape of the effect structures 300 or aseparate scan used only to determine the effect structure 300orientation. Starting with the sample 505, a measurement area 510 isidentified that extends across the boundary 515 of the visual effect 360and the portion of the sample 505 that does not include the visualeffect 360. The sample's CT scan data is segmented, using an intensitythreshold, into 3D voxel blobs which will be considered candidates forthe effect structures 300. The previously determined shape parametersare then used to refine the voxel blobs, such as to separate voxel blobsrepresenting effect structures 360 from voxel blobs that were caused bynoise, artifacts, etc. An effect structure normal vector ESNV (as shownin FIG. 17) is calculated for each effect structure 360 and is comparedin the plane perpendicular to the boundary 515 (or perpendicular to thetangent of the boundary at the center of the boundary 515 in the sample)of the visual effect 360 to an outer surface normal vector OSNV of theouter surface 133 of the article 100. If the angle between the ESNV andOSNV is obtuse, the direction of the ESNV should be reversed making themeasured angle acute. The OSNV at a surface point of the article shouldbe extended towards the effect structure 300 until it intersects aneffect structure 300 with an ESNV. The acute angle between the ESNV andOSNV is recorded for that point.

As shown in FIG. 18, the angles between the effect structure normalvector ESNV and the outer surface normal vector OSNV for each point onthe outer surface 133 of the article 100 in each is measured andaveraged across the width of the measurement area 510. The averages areplotted as a first curve, such as that shown in FIG. 19, and themagnitude (absolute value) of the averages are plotted on a secondcurve, as shown in FIG. 20.

The maximum and minimum values are identified from the magnitude on thesecond curve. As shown in FIG. 18, an inner square averaging area 530from the sample is defined within the visual effect 360 and one isdefined close to, but located outside of the visual effect 360. Theinner square averaging area 530 within the visual effect 360 is centeredon the location of the maximum average magnitude as identified from thesecond curve. Averaging the acute angles between the ESNV and OSNVwithin this square area provides an Average Normal Orientation for theeffect structures 300 within the visual effect 360. A outer squareaveraging area 531 is defined outside of the visual effect 360 centeredon the location of the minimum averaged magnitude as identified from thesecond curve. Averaging the acute angles between the ESNV and OSNVwithin this square area provides an Average Normal Orientation for theeffect structures 300 outside of the visual effect 360. The AverageNormal Orientation of the effect structures 300 within the visual effect360 is compared to the Average Normal Orientation of the effectstructures outside of the visual effect 360. The absolute differencebetween the two Average Normal Orientation values gives the LocalOrientation Index (“LOI”) for the visual effect 360.

It should be noted that in some embodiments, a minimum can also beidentified that is located within the visual effect 360. This minimum isignored for the purpose of determining the LOI of the region within thevisual effect 360 adjacent the boundary 515 versus an area outside thevisual effect 360, but may be used to calculate the LOI of a regionwithin the visual effect 360 not adjacent the boundary 515 versus anarea outside the visual effect 360.

Further details related to the methods for measuring Average NormalOrientation and Local Orientation Index are set for in the Example,below.

95% Delta E Value Measurement Method:

To measure the 95% Delta E Value of a visual effect disposed on anarticle, a sample, such as sample 600 shown in FIGS. 21A-21N, must beidentified that includes the visual effect 360 to be analyzed. This canbe done by visually locating the visual effect 360 to be analyzed,preferably in an area of low curvature on the article 100. The sample600 must include both a cavity region 330 and a non-cavity region 333.At least 10% of the sample 600 must be made up of cavity region 330 andat least 10% of the area of the sample 600 must be made up of non-cavityregion 333. The sample 600 should also include a continuous rectangulararea of about 0.135 in² (87.1 mm²) that is visibly free of noise andartifacts. This area, the area of analysis AOA, is analyzed to determinea 95% Delta E Value for the visual effect, as set forth herein.

The sample 600 is prepared by cutting a rectangular piece from the wallof an article in such a fashion that the sample is nearly flat. Forexample, if the bottle is a cylinder, a rectangular shape with long axisparallel to the height axis of the cylinder will reduce the curvature ofthe final sample. To obtain the sample 600, sharp scissors (or othercutting means that will not destroy the sample piece itself) are used tofirst cut a piece from the article wall that is approximately double thedesired dimensions of the portion of the sample to be analyzed. A sharpsingle edge, GEM polytetrafluoroethylene (PTFE) coated stainless steelrazor blade such as available from Electron Microscopy Sciences, 1560Industry Road, Hatfield, Pa. 19440 (item #71970), or the like, is usedto carefully trim the sample down to the desired dimensions. The sample600 can be any suitable size so long as it includes a continuousrectangular area of analysis AOA of about 0.135-inch squared that isfree of noise and artifacts. The sample 600 is backed with a whitebacking 610, specifically, the white half of the 2856 Byko-chartBrushout 5DX card available from BYK-Gardner, Germany, or an equivalenthaving L*>93, −2<a*<2, and −2<b*<2. The backing 610 is placed againstthe portion of the sample 600 that corresponds to the inner surface ofthe article. The backing 610 should be sized to at least cover the scanfield 620, in this example a 1-inch by 1-inch (2.54 cm by 2.54 cm) area.The sample 600 is conditioned at about 23° C.±2 C.° and about 50%±2%relative humidity for 2 hours prior to analysis.

A flatbed scanner capable of scanning a minimum of 24 bit color at 1200dpi with manual control of color management (a suitable scanner is anEpson Perfection V750 Pro from Epson America Inc., Long Beach Calif., orequivalent) is obtained and calibrated, as set forth herein. The scanneris interfaced with a computer running color calibration software capableof calibrating the scanner against a color reflection IT8 targetutilizing a corresponding reference file compliant with ANSI methodIT8.7/2-1993 (suitable color calibration software is Monaco EZColor ori1Studio available from X-Rite Grand Rapids, Mich., or equivalent). Thecolor calibration software constructs an International Color Consortium(ICC) color profile for the scanner, which is used to color correct anoutput image using an image analysis program that supports applicationof ICC profiles (a suitable program is Photoshop available from AdobeSystems Inc., San Jose, Calif., or equivalent). The color correctedimage is then converted into the CIE L*a*b* color space for subsequentcolor analysis (a suitable image color analysis software is MATLABversion 9.5 available from The Mathworks, Inc., Natick, Mass.).

The scanner is turned on 30 minutes prior to calibration and imageacquisition. Any automatic color correction or color management optionsincluded in the scanner software are turned off (de-selected). If theautomatic color management cannot be disabled, the scanner is notappropriate for this application. The procedures recommended by thecolor calibration software are followed to create and export an ICCcolor profile for the scanner.

The sample 600 is carefully laid flat on the center of the scanner glasswith the outer surface (opposite of the white backing) oriented towardthe glass. A scan is taken that completely contains the AOA and isimported into the image analysis software at 24 bit color with aresolution of 1200 dpi (approximately 47.2 pixels per mm) in reflectancemode. The ICC color profile is assigned to the image producing a colorcorrected sRGB image. This calibrated image is saved in an uncompressedformat to retain the calibrated R, G, B color values, such as a TIFFfile, prior to analysis. A second scan of the sample 600 is acquired byrotating the sample 600 by 90 degrees relative to the axis perpendicularto the major surface of the sample 600 and repeating the procedureabove.

The sRGB color calibrated image is opened in the color analysis softwaresuch as MATLAB which converts it into CIE L*a*b* color space. This isdone as follows: First, the sRGB data is scaled into a range of [0, 1]by dividing each of the values by 255. Second, the companded sRGBchannels (denoted with upper case R, G, B), or generically “V” arelinearized (denoted with lower case r, g, b), or generically “v” as thefollowing operation is performed on all three channels (R, G, and B):

V ∈ {R, G, B} v ∈ {r, g, b} $v = \begin{Bmatrix}\frac{V}{12.92} & {{{if}\mspace{14mu} V} \leq 0.04045} \\\left( \frac{V + 0.055}{1.055} \right)^{2.4} & {otherwise}\end{Bmatrix}$

The linear r, g, and b values are then multiplied by a matrix to obtainthe XYZ Tristimulus values according to the following formula:

$\begin{bmatrix}X \\Y \\Z\end{bmatrix} = {\begin{bmatrix}0.4124 & 0.3576 & 0.1805 \\0.2126 & 0.7152 & 0.0722 \\0.0193 & 0.1192 & 0.9505\end{bmatrix}\begin{bmatrix}r \\g \\b\end{bmatrix}}$

The XYZ Tristimulus values are rescaled by multiplying the values by100, and then converted into CIE 1976 L*a*b* values as defined in CIE15:2004 section 8.2.1.1 using D65 reference white.

The CIE L*a*b* image is analyzed by cropping out the AOA for colorcomparison. The AOA should be chosen to avoid noise in the sample causedby dirt, scratches, defects, etc. and any defects, noise or dirt relatedto the scanner. An image with noise that covers more than about 5% ofthe total area is not suitable for analysis. The AOA used for theanalysis of each sample 600 should be between 190,000 and 200,000 totalpixels (for example, about 400 pixels by about 500 pixels).

The L*, a*, and b* values for each pixel within the AOA are comparedwith the L*, a*, and b* values for every other pixel in the AOA. A DeltaE is computed for each comparison using the following equation:

Delta E _(i,j)=√{square root over ((L _(i) *−L _(j)*)²+(a _(i) *−a_(j)*)²+(b _(i) *−b _(j)*)²)}

For each pixel ‘i’, Delta E is calculated for every pixel ‘j’ not equalto ‘i’.

A cumulative histogram of these Delta E values is divided by the totalnumber of Delta E measurements. The bin size of the cumulative histogramis set equal to 0.1. The last bin value will be 1, which represents 100%of the Delta E measurements. The largest bin value less than 95% isrecorded as the “95% bin value” for the sample to ignore any remainingnoise in the image.

Each sample 600 is scanned twice, differing by a 90-degree rotation asdescribed earlier. Separate cumulative histograms and 95% bin values aregenerated for each scan. The maximum of the two 95% bin values for eachsample 600 is recorded as the “95% Delta E Value” for the sample 600.

Root Mean Square Roughness (Sq):

Root Mean Square Roughness, Sq, is measured using a 3D Laser ScanningConfocal Microscope such as a Keyence VK-X200 series microscopeavailable from KEYENCE CORPORATION OF AMERICA) which includes a VK-X200Kcontroller and a VK-X210 Measuring Unit. The instrument manufacturer'ssoftware, VK Viewer version 2.4.1.0, is used for data collection and themanufacturer's software, Multifile Analyzer version 1.1.14.62 and VKAnalyzer version 3.4.0.1, are used for data analysis. If needed, themanufacturer's image stitching software, VK Image Stitching version2.1.0.0, can be used. The manufacturer's analysis software is compliantwith ISO 25178. The light source used is a semiconductor laser with awavelength of 408 nm and having a power of about 0.95 mW.

The sample to be analyzed is obtained by cutting a piece of the articleout of the article that includes the region to be analyzed in a sizethat can fit the microscope for proper analysis. To measure Sq of anetched portion of an article, a sample should be obtained that includesan etched region and the analysis should take place only over theportion of the sample that is etched. If the sample is not flat, but isflexible, the sample may be held down on the microscope stage with tapeor other means. If, due to the shape, flexibility or othercharacteristic of the sample, measurements will be more accurate whenthe sample is not flattened, corrections may be sued, as explainedhereinbelow.

The measurement data from the sample is obtained using a 20× objectivelens suitable for non-contact profilometry, such as a 20× Nikon CF ICEpi Plan DI Interferometry Objective with a numerical aperture of 0.40.The data is acquired using the acquisition software's “Expert Mode”,with the following parameters set as described here: 1) Height ScanRange is set to encompass the height range of the sample (this can varyfrom sample to sample depending on the surface topography of each); 2)Z-direction Step Size is set to 0.50 micrometers; 3) Real Peak Detectionmode is set to “On”; and 4) Laser Intensity and Detector Gain areoptimized for each sample using the autogain feature of the instrumentcontrol software.

Prior to analysis, the data is subjected to the following correctionsusing the manufacturer's Multifile Analyzer software: 1) 3×3 mediansmoothing in which the center pixel of a 3×3 pixel array is replaced bythe median value of that array; 2) noise removal using weak height cut(following built in algorithm in the analysis software), and 3) shapecorrection using waveform removal (0.5 mm cutoff). The Reference Planeis specified using the Set Area method and selecting the same area as isused for the shape removal. Regions including foreign materials,artifacts of the sample harvesting process or any other obviousabnormalities should be excluded from analysis and alternative samplesshould be used any sample can't be accurately measured. The resultingvalue is the Root Mean Square Roughness, Sq, for the measured portion ofthe sample.

Sz—Maximum Peak/Pit Height:

Sz, the Maximum Peak/Pit Height, is measured using a 3D Laser ScanningConfocal Microscope such as a Keyence VK-X200 series microscopeavailable from KEYENCE CORPORATION OF AMERICA) which includes a VK-X200Kcontroller and a VK-X210 Measuring Unit. The instrument manufacturer'ssoftware, VK Viewer version 2.4.1.0, is used for data collection and themanufacturer's software, Multifile Analyzer version 1.1.14.62 and VKAnalyzer version 3.4.0.1, are used for data analysis. If needed, themanufacturer's image stitching software, VK Image Stitching version2.1.0.0, can be used. The manufacturer's analysis software is compliantwith ISO 25178. The light source used is a semiconductor laser with awavelength of 408 nm and having a power of about 0.95 mW.

The sample to be analyzed is obtained by cutting a piece of the articleout of the article that includes the region to be analyzed in a sizethat can fit the microscope for proper analysis. To measure Sz of anarticle with etched and non-etched regions 113, a sample should beobtained that includes both the etched and non-etched regions 113. Theanalysis should take place over both the etched and non-etched regions113. If the etched region has one axis that is longer than another, thelong axis of the etched region to be measured should be orientedapproximately perpendicular to the long axis of the image region. If thesample is not flat, but flexible, the sample may be flattened and helddown on the microscope stage with tape or other means. If, due to theshape, flexibility or other characteristic of the sample, measurementswill be more accurate when the sample is not flattened, corrections maybe used, as explained hereinbelow.

Sz is obtained by acquiring and stitching together several contiguousimages of the sample in the region of interest (e.g. a region includingboth etched and non-etched areas). The images are collected using 10×objective lens suitable for non-contact profilometry such as a 10× NikonCF IC Epi Plan DI Interferometry Objective with a numerical aperture of0.30, giving an image area of approximately 1430×1075 micrometers perimage. The images are automatically stitched using the manufacturer's“VK Image Stitching” software. Data is acquired from the images usingthe acquisition software's “Expert Mode” wherein the followingparameters are set as described herein: 1) Height Scan Range is set toencompass the height range of the sample (this can vary from sample tosample depending on the surface topography of each); 2) Z-direction stepsize is set to 2.0 micrometers; 3) Real Peak Detection mode is set to“On”; and 4) Laser Intensity and Detector Gain are optimized for eachsample using the autogain feature of the instrument control software.

Prior to analysis, the data is subjected to the following correctionsusing the manufacturer's Multifile Analyzer software: 1) 3×3 mediansmoothing in which the center pixel of a 3×3 pixel array is replaced bythe median value of that array; 2) noise removal using strong height cut(following built in algorithm in the analysis software), and 3) shapecorrection using the simplest method (plane, second order curve orwaveform removal) sufficient to remove the shape of the surface. Regionsincluding foreign materials, artifacts of the sample harvesting processor any other obvious abnormalities should be excluded from analysis andalternative samples should be used any sample can't be accuratelymeasured. The shape of the surface is removed using the Waveform Removalmethod of the Surface Shape Correction tool. The cutoff wavelength isspecified to be approximately five times the size of the largeststructure to be preserved. The Reference Plane is specified using theSet Area method and selecting the same area as is used for the shaperemoval. The resulting value is the Sz for the measured portion of thearticle.

Example 1—Local Orientation Index

First, an article is obtained that includes effect structures in atleast a portion of the wall of the article. A sample portion of thearticle is identified by visually locating a visual effect on thearticle. The sample to be analyzed is prepared by cutting a rectangularpiece from the wall of an article. The sample is centered such that theboundary of the visual effect is generally parallel to the shortdimension of the sample. The sample includes portions of the articlethat include the visual effect and portions that do not include thevisual effect so as to ensure the boundary of the visual effect areincluded in the sample. In this example, the sample included the fullwidth of the visual effect including boundaries on either side of thevisual effect and approximately 0.5 mm outside the visual effect. It isnot critical that the sample span entirely across the visual effect. Toobtain the sample, sharp scissors (or other cutting means that will notdestroy the sample piece itself) are used to first cut a piece from thearticle wall that is approximately double the desired dimensions of thesample to be measured. In this example, a piece of the bottle in thesize of about 2.6 mm×7 mm is cut from the bottle wall. A sharp singleedge, GEM polytetrafluoroethylene (PTFE) coated stainless steel razorblade such as available from Electron Microscopy Sciences, 1560 IndustryRoad. Hatfield, Pa. 19440 (item #71970), or the like, is used tocarefully trim the sample down to the desired dimensions, in thisexample, approximately 1.3 mm×3.5 mm.

The sample is then subjected to X-ray tomographic microscopy scanningusing a synchrotron light source. The scanning for this example isperformed at the TOmographic Microscopy and Coherent rAdiologyexperimentTs (TOMCAT) beamline of the Swiss Light Source (SLS) at thePaul Scherrer Institute (PSI, Switzerland). The sample is centrallypositioned on a suitable mount (e.g. a 12 mm diameter mount) and adheredto its surface with black double-sided adhesive tape or an alternativesuitable adhesive. A superficial fiducial mark on the corner of eachsample is used to orient each sample verses the x-ray beam when therotation stage is at 0 degrees. X-rays are convened to visible light byusing a LuAG:Ce 20 μm scintillator, magnified with a 20× objective usinga high-quality microscope such as an Opaque Peter, Lentilly, France,with a 20× objective and detected by a sCMOS camera (PCO.Edge 5.2, PCO,Kelheim, Germany). The instrument's image acquisition settings areselected such that the image intensity contrast is sensitive enough toprovide clear and reproducible discrimination of the sample structuresfrom the air and the surrounding mount. The instrument is operated withthe following settings: energy setting 19 keV, 1500 projections, 0.815mm horizontal field of view with 0.688 mm vertical height, 250 msexposure time and a resulting isotropic voxel size of 0.3186 μm. Thespecific image acquisition settings and contrast mode are optimized toachieve the necessary contrast discrimination and a suitable resolutionto continue analysis.

The scans are acquired with a multi-overlap method to precisely positioneach of 6 high resolution scans in a sequence to cover the length ofsample (˜3.5 mm) from edge to edge. The scan sequence is centered in themiddle of sample with an overlap area approximately 0.24 mm betweenscans. Where the sample thickness (caliper) is larger than the slicestack height, a second stack scan sequence is acquired to cover theremaining sample thickness. When these data sets are merged byregistering the overlapping areas, a contiguous composite of the entirelength of the sample and its thickness is provided. Each scan of thesample is captured such that a similar volume is included in the datasetwith dimensions of 2560×2560×2160. Tomographic reconstructions areperformed using the Gridrec algorithm (F. Marone and M. Stampanoni,“Regridding reconstruction algorithm for real time tomographic imaging,”J. Synchrotron Rad., vol. 19, pp. 1029-1037, 2012.) and thereconstructed tomography slices provided in 16-bit TIF format.

Software suitable for subsequent image processing steps and quantitativeimage analysis includes programs such as Avizo Light 2019.1(Visualization Sciences 25 Group/FEI Company, Burlington, Mass.,U.S.A.), and MATLAB with corresponding MATLAB “Image Processing Toolbox”(The Mathworks Inc. Natick, Mass., U.S.A.). In this example, theSynchrotron data is collected with a grey level intensity depth of16-bit and is converted to a grey level intensity depth of 8-bit, takingcare to ensure that the resultant 8-bit dataset maintains the maximumdynamic range and minimum number of saturated voxels feasible, whileexcluding extreme outlier values.

A slice of the continuous composite data matrix representingapproximately 0.05×3.6×1.3 mm of the sample volume is used to determinethe shape parameters of the effect structures. In this example, theeffect structures which are added to the resin (Iriodin® 123 from MerckKGaA, Darmstadt, Germany) appear as platelets when visualized. At avoxel resolution of 318.6 nanometers, the resulting dataset isapproximately 160×11500×4100 voxels. The density of the effectstructures is sufficiently different from the density of the plasticthat an intensity threshold can be determined using an automatedtechnique known as Otsu method: Otsu, N., “A Threshold Selection Methodfrom Gray-Level Histograms,” IEEE Transactions on Systems, Man, andCybernetics, Vol. 9, No. 1, 1979, pp. 62-66, which is implemented byMATLAB's “Multithresh” function. Collections (“blobs”) of adjacentvoxels that exceed the intensity threshold are numerical labeled using aconnected components method such as the method available in MATLAB's“Bwconncomp” using a connectivity of 6. Blobs at the borders of datasetor near the edges of the bottle are eliminated.

Small blobs, some with a volume of single voxel, can be caused by noisein the acquisition system. Blobs with volumes less than or equal to 236voxels make up only 5% of the total blob volume. These small blobs areeliminated from the analysis.

The voxel positions of a blob are passed as a cloud of points to athree-dimensional ellipsoidal fitting algorithm, such as the“regionprops3” function found in MATLAB. “Regionprops3” is requested toreturn the length in voxels of the ellipsoidal axes using the“PrincipalAxisLength” property. The smallest axis length corresponds tothe thickness of the effect structures. In this example, a histogram ofblob thicknesses is unimodal and shows that more than 98% had athickness of 2 microns or less. Blobs greater than 2 microns areinterpreted as touching platelets, artifacts, etc. and are eliminatedfrom the data set. A thickness of 2 microns corresponds to themanufacturer's maximum thickness specification. The average thickness ofthe remaining blobs is 1.2 microns.

The aspect ratio of an effect structure is the ratio of its longest axisdivided by its shortest axis. The larger the aspect ratio, the flatterthe effect structure. In this example, a cumulative histogram of theaspect ratio shows an inflection at a value of about 4. Only 5% of theremaining blobs have an aspect ratio of less than 4. Thickness andaspect ratio, as described herein, were used to identify platelet blobs.In this example, blobs identified as platelets using the criteriadescribed accounted for 90% of the starting blob volume.

An average thickness of 1.2 microns and an aspect ratio of at least 4results in a minimum long dimension of about 5 microns. The samplevolume for the angle analysis is increased to approximately 0.1×3.6×1.3mm which assured multiple effect structures across the sample. At avoxel resolution of 318.6 nanometers, this results in a dataset ofapproximately 320×11500×4100 voxels. Assuming XYZ coordinates, the YZplane cuts across a single visual effect in the article. The thicknessof the article wall is measured along the Z axis. An effect structurewith an effect structure normal vector (“ESNV”) identical to the Z axisis nearly parallel to the XY plane.

In this example, the article is a bottle with an overall shape thatapproximates a cylinder. A visual effect parallel to the height axis ofthe cylinder was identified by visual inspection of the article. Thesample was cut across the visual effect and therefore appears as an arcof a cylinder. The top of the outer surface of the sample was fitted toa circular arc using a middle YZ slice from the data set in the Xdirection. Visual inspection of XZ slices along the Y axis showed thatthe surface of the sample remained nearly constant in the X directionfor this very narrow region. An arc fitted to the middle slice couldtherefore be replicated through all the YZ slices.

To determine an arc of the sample and the outer surface normal vectors(“OSNV”), an arc of less than 6 degrees was fitted using trial and errorwhere each trial arc sampled the middle YZ slice voxel along the arc andcalculated an average voxel value. The synchrotron data includes brightvoxels along the interface of the plastic with the air due todiffraction affects. An arc mask 7 voxels wide (˜2 microns) is generatedand used as a template to calculate an average voxel value. At aminimum, the circular arc should touch the sample edge within a 5%distance from the end points and within a 10% distance from the arccenter. Trial arcs of various sizes and displacements may be testedalong with the maximum average voxel value to choose the final arc. Theparameters of the fitting arc including its center are stored for laterreference. The arc mask is extended towards the center to create aregion of interest for effect structure measurements. The region ofinterest is also copied to all the YZ slices. The original fitting arcis subtracted from the region of interest to prevent edge diffractionvoxels from being mis-labelled as effect structure voxels.

To find the effect structures, a threshold is determined by MATLAB's“Multithresh” function using voxels within the arc mask. Collections ofadjacent voxels that exceed the intensity threshold are labeled ascandidate effect structures. Candidate effect structures are tested fora volume at least 237 voxels, a thickness of no more than 2 microns andan aspect ratio of at least 4. An ESNV is determined using anellipsoidal fit provided by the “regionprops3” function found in MATLABusing the “EigenVectors” property. The eigen vector corresponding to thethickness of the effect structure is projected to the YZ plane and usedas the ESNV. Any effect structure that crosses outside of the region ofinterest is eliminated from the analysis.

The OSNV on the outer surface of the bottle is a ray that runs from apoint on the arc to the center of the fitting arc circle. Thus, the OSNVlies on the YZ plane. The OSNV for each point on the article is comparedto the ESNV of the effect structure directly beneath it in the YZ planealong the path of the ray. A line is drawn from the surface point usingthe straight edge of the surface normal to the first intersecting effectstructure. A line that penetrates at least 90% of the sample withoutcrossing an effect structure is flagged as a missed crossing and isignored.

The acute angle between the OSNV and the ESNV is determined in the YZplane. The surface of the sample can be defined as two-dimensional arraywhere the width will represent one dimension and the arc length willrepresent the second dimension. Furthermore, the surface can define aone-dimensional first curve, if the angle between OSNV and ESNV isaveraged within the voxel columns across the width dimension. This firstcurve, shown in FIG. 19 and representing Sample 2, gives an averageangle between the article surface and the underlying effect structuresas one moves across the visual effect. The absolute values or magnitudeof the average angles is plotted as a second curve starting outside ofthe visual effect and proceeding across the boundary of the visualeffect into the visual effect (for the first border). The same was donefor the other border of the visual effect (the second border). Note thatthe averaging ignores missed crossings. The second curve, againrepresenting Sample 2, is shown in FIG. 20. A maximum absolute averagevalue can be located from the second curve.

An averaging region of interest is defined as 100 microns×100 micronssquare that spans the width of the sample. The average should excludemissed crossings and is herein referred to the Average NormalOrientation of the effect structures within the square region ofinterest. The maximum average located from the magnitude curve is takenas the center of the square region of interest and should fall withinthe visual effect. Examining the curve, from the maximum locationtowards the nearest end point outside of the visual effect can be usedto locate a minimum absolute average value. The minimum location ischosen as the center-point for a 100 micron×100 micron region ofinterest outside the visual effect. If the minimum location is too closeto the sample edge or to the visual effect to allow for 100 micronsquare area to be taken entirely outside the visual effect and withinthe sample area then the next lowest value on the curve outside thevisual effect is chosen as the minimum. This process may need to berepeated until a 100 micron×100 micron region of interest outside thevisual effect and within the sample area is defined. A Local OrientationIndex for the sample is determined by calculating the absolutedifference between the Average Normal Orientation of the effectstructures within the visual effect and the Average Normal Orientationof the effect structures outside of the visual effect. For Sample 2, theLocal Orientation Index for the first border is 11.6 and the secondborder is 11.3.

The results from three different bottles are shown in Table 1, below.Each sample included a visual effect 360 with two borders 515. However,it should be understood that any particular sample may include only aportion of a visual effect 360, such that it has only one border 515.The difference between the samples relates to the depth of the etch madein the preform that corresponds to the visual effect in the article. Inaddition, a prophetic example (Sample 4) is included to show the resultsof a bottle that includes effect structures, but for which there hasbeen no selective modification of the orientation corresponding with avisual effect. Accordingly, it is expected that the Average NormalOrientation of the effect structures will be generally the samethroughout the walls of the article and similar to that of Samples 1-3.The bottle of Sample 4 has a generally smooth outer surface.

TABLE 1 Average Average Sz of Normal Normal Local Outside EtchOrientation Orientation Orien- Surface Depth Inside Outside tation ofSample (μm) Visual Effect Visual Effect Index Bottle Sample 1 434 26.70.5 27.2 17.2 Border 1 Border 2 −28.1 0.6 28.7 Sample 2 219 10.9 −0.711.6 8.7 Border 1 Border 2 −11.0 0.3 11.3 Sample 3 84 7.9 0.5 7.4 6.5Border 1 Border 2 −7.1 −1.4 5.7 Sample 4 0 N/A - no 0.8 0 5.0 VisualEffect.

Samples 1-3 are made according the ISBM process described herein. TheISBM process starts with making a preform. The preform is molded byparallel co-injection process. The resin blend for the ISBM processcontains a thermoplastic resin and effect pigments. The raw materialsfor the blend are dried prior to processing. The dried blends are fedusing a hopper mounted on a plasticizing screw extruder (single-screwdesign) where the stream of hot polymer melt enters the mold cavity. Asingle-cavity preform mold on a Fanuc Roboshot S-2000i275B injectionmolding machine is used to make performs from the molten discharge at abarrel temperature of about 270-310° C., and a part mold size of about54.5 grams with mold cooling at about 13° C. The preform is ejected fromthe mold and allowed to cool at ambient conditions.

Once cooled, the preform is etched by a laser to create a predeterminedpattern of cavities on the outer surface of the preform. A sealed carbondioxide type laser is used which has power in the range of 40 W to 2.5kW, and a laser wavelength of 9 microns to 11 microns. An example ofsuch a laser is the LPM1000 laser available in LASERSHARP systems fromLasX Industries, Inc. of White Bear Lake, Minn., United States. Thethree sample preforms are etched at three different laser parameters:3000, 6000 and 9000, as shown in Table 1.

After etching the preform is placed in a 2-stage re-heat Stretch BlowMolding (SBM) machine, such as a Sidel™ SBO 2/10 Universal blow moldingmachine. The cooled preform is heated above the polymer softeningtemperature (Tg) using an infrared machine to about 100 to about 110° C.for about 2 minutes (called the “reheat” stage). The softened preform isthen put into a container mold, a mechanical stretch rod is insertedinto the preform to guide and stretch the preform in the axialdirection. Pressurized air is introduced in two steps: as a pre-blow ofabout 10-12 bar for about 0.12 seconds followed by a second-blow ofabout 35-38 bar to complete the blow molding of the bottle at a blowmold temperature of about 17° C. The stretch ratio (axial to hoop) ofthe final article is about 8:1.

Table 2, below, provides additional details about the makeup of thepreform and the etching parameters of Samples 1-3.

TABLE 2 Sample 1 Sample 2 Sample 3 PET + 10% masterbatch PET + 10%masterbatch PET + 10% masterbatch containing Iriodin ® 123 containingIriodin ® 123 containing Iriodin ® 123 (approximately 30% (approximately30% (approximately 30% Preform loading) plus secondary loading) plussecondary loading) plus secondary Composition color toner color tonercolor toner Etching 3000 6000 9000 Parameters Depth of 434 219 84 Etch(μm)

Example 2: 95% Delta E Value

Samples 1-6 were taken from six different PET blow molded bottles, inaccordance with the 95% Delta E Value measurement method set forthherein. Each sample had at least one visual effect 360 corresponding toan etched region of the preform from which the article was made.Accordingly, each visual effect 360 included adjacent cavity andnon-cavity regions disposed on the outer surface of an article asdescribed herein. The different samples had visual effects that differedin shape color and/or contrast. A control sample, Sample 7, was alsomeasured. The control sample was taken from a clear PET blow moldedbottle which was formed from a preform that was not etched. As such, thecontrol sample did not include a visual effect having adjacent cavityand non-cavity regions. The Delta E of the sample was measured inaccordance with the method set forth herein and the 95% Delta E Valuewas determined. The control sample was analyzed the same way as theother samples, but no visual effect was identified or analyzed. Rather,just a clean, conditioned sample was analyzed. The results of theanalysis are set forth in Table 3, below.

TABLE 3 Avg 95% Max Sample Sample AOA AOA Delta Delta E Delta NumberName (pixels) (inches{circumflex over ( )}2) E Value E 1 Blue lines193600 0.134 5.6 12.0 40.8 1 Blue lines - 193600 0.134 1.7 3.4 30.9 90deg 2 Cloud 192700 0.134 5.4 13.2 28.2 2 Cloud - 191350 0.133 4.2 8.615.9 90 deg 3 Green leaf 192000 0.133 3.0 5.5 13.8 3 Green Leaf - 1920000.133 3.0 5.3 26.0 90 deg 4 Red pattern 193600 0.134 12.1 29.2 56.2 4Red pattern - 193600 0.134 15.3 34.2 61.3 90 deg 5 White lines 1936000.134 4.4 11.0 20.7 5 White lines - 191100 0.133 4.3 8.8 16.2 90 deg 6White pattern 192000 0.133 2.4 5.0 18.8 6 White pattern - 192000 0.1334.9 13.7 24.8 90 deg 7 Control 192400 0.134 1.4 2.6 36.4 7 Control -192400 0.134 1.4 2.7 27.8 90 deg

Table 4 shows the information from Table 3 that represents the maximumvalue of the Average Delta E, 95% Delta E, and Max Delta E for each ofthe samples.

TABLE 4 95% Sample Avg Delta E Max Number Sample Name Delta E ValueDelta E 1 Blue Lines 5.6 12.0 40.8 2 Cloud 5.4 13.2 28.2 3 Green Leaf3.0 5.5 26.0 4 Red Pattern 15.3 34.2 61.3 5 White Lines 4.4 11.0 20.7 6White Pattern 4.9 13.7 24.8 7 Control 1.4 2.7 36.4

Table 5 is a summary of the information in Tables 3 and 4 showing thefinal 95% Delta E Value for each sample. As can be seen, the controlsample, Sample 7, had a 95% Delta E Value of less than 3.0 and all othersamples have 95% Delta E Values greater than 3.0. In fact, all of thesamples other than the control have 95% Delta E Values greater than 5.0,and specifically greater than or equal to 5.5. Additionally, all of thesamples other than the control had 95% Delta E Values between 3.0 and350, and more specifically between 5.0 and 100.0.

TABLE 5 Sample Number Sample Name 95% Delta E Value 1 Blue lines 12.0 2Cloud 13.2 3 Green leaf 5.5 4 Red pattern 34.2 5 White lines 11.0 6White pattern 13.7 7 Control 2.7

All percentages are weight percentages based on the weight of thecomposition, unless otherwise specified. All ratios are weight ratios,unless specifically stated otherwise. All numeric ranges are inclusiveof narrower ranges; delineated upper and lower range limits areinterchangeable to create further ranges not explicitly delineated. Thenumber of significant digits conveys neither limitation on the indicatedamounts nor on the accuracy of the measurements. All measurements areunderstood to be made at about 25° C. and at ambient conditions, where“ambient conditions” means conditions under about one atmospherepressure and at about 50% relative humidity.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A blow molded article formed from a preformhaving an exterior surface including at least one etched region and atleast one non-etched region, the article comprising: a body portionincluding one or more walls surrounding an interior space, the one ormore walls having an article inner surface, an article outer surface,and a wall thickness; a cavity region disposed on a portion of thearticle outer surface, the cavity region corresponding to the etchedregion in the preform; and a non-cavity region disposed on a portion ofthe article outer surface and adjacent the cavity region; wherein theadjacent cavity and non-cavity regions form one or more visual effects,and wherein at least one of the one or more visual effects includes aportion having a 95% Delta E Value of at least 3.0.
 2. The blow moldedarticle of claim 1 wherein at least one of the one or more visualeffects includes a portion having a 95% Delta E Value of at least 5.0.3. The blow molded article of claim 1, wherein at least one of the oneor more visual effects includes a portion having a 95% Delta E Value ofgreater than or equal to 5.5.
 4. The blow molded article of claim 2wherein at least one of the one or more visual effects includes aportion having a 95% Delta E Value of between 5.0 and 100.0.
 5. The blowmolded article of claim 1 wherein the visual effect is a dimensionalvisual effect.
 6. The blow molded article of claim 1 wherein the etchedregion includes one or more etches that form a three-dimensional patternon the preform.
 7. The blow molded article of claim 6 wherein the visualeffect has a shape that corresponds generally to the three-dimensionalpattern of the preform.
 8. The article of claim 1 wherein the etchedregion and the non-etched region create a topography on the articleouter surface, the topography having a Maximum Peak/Pit Height, Sz, lessthan 750 microns.
 9. The article of claim 8 wherein the topography onthe outer surface has a Maximum Peak/Pit Height, Sz, less than 250microns.
 10. The article of claim 1 wherein the article includes a labeldisposed at least partially over the portion of the article outersurface corresponding to the visual effect.
 11. The article of claim 1wherein the etched region has a Root Mean Square Roughness of less thanor equal to 10 microns.
 12. The article of claim 11 wherein the etchedregion has a Root Mean Square Roughness of less than or equal to 2microns.
 13. The article of claim 1 wherein the one or more wallsinclude a first layer and a second layer, wherein the first layer is adifferent from the second layer.
 14. The article of claim 13 wherein thedifference between the first layer and the second layer is selectedfrom: color, material, thickness, additive, pigment, opacity, gloss,optical property, amount of recycled material, type of recycledmaterial, or strength.
 15. The article of claim 1 wherein the wallthickness varies in at least the portion of the wall including thevisual effect.
 16. A method for making a blow molded article from apreform, the method comprising the following steps: a) providing apreform of a thermoplastic material, the preform having a body with oneor more walls and an opening, wherein at least a portion of the one ormore walls of the preform is etched to form a three-dimensional patternof cavities thereon; and b) blow molding the preform to form a blowmolded article having cavity regions and non-cavity regions thattogether form one or more visual effects in at least one wall of theblow molded article, at least one of the one or more visual effectsincludes a portion having a 95% Delta E Value of at least 3.0.
 17. Themethod of claim 16 wherein the three-dimensional pattern of cavities isformed by: thermal-etching, mechanical etching, laser etching, chemicaletching, preform mold design, and combinations thereof.
 18. The methodof claim 16 further including the step of applying a label or printingto the portion of the outer surface that corresponds to the visualeffect, does not correspond to the visual effect, or both.
 19. Themethod of claim 16 wherein the blow molded article has a first layer anda second layer, wherein the first layer is disposed outwardly of thesecond layer and includes a portion that is translucent or transparent.20. The method of claim 16 wherein the preform includes surfaceprinting, wherein the surface printing is selected from: laser printing,ink jet printing, contact printing, screen printing, lithographicprinting or combinations thereof.